Novel metal complexes

ABSTRACT

Metal phenolates having at least one piperidinyl group sterically hindered on the nitrogen atom are suitable as additives for organic material.

The present invention relates to novel metal complexes of metal cationshaving a double or triple charge with a chelate-forming anion containingphenolate groups, the preparation of these complexes and their use aslight stabilisers in organic material, and also to the organic materialprotected with the aid of these complexes.

Metal complexes with sterically hindered amines and anions having asingle charge have been described as stabilisers for synthetic polymersin German Offenlegungsschrift No. 2,625,967. These complexes aremixtures of metal salts and sterically hindered amines.

Novel metal chelate complexes have now been found which aredistinguished by a good light-stabilising action and good stability toextraction and have a good compatibility in polymers.

The novel metal complexes are of the general formula I

    [M.sup.q⊕ ][L.sup.r⊖ ].sub.(q-s)/r [B.sup.⊖ ].sub.s ·m A                                             (I)

in which M is a metal ion having a double or triple positive charge, qis 2 or 3 and L is a t-dentate chelate-forming anion which contains 1 or2 phenolate groups and which contains at least one group of the formulaeIIa or IIb ##STR1## in which t is 2, 3 or 4 and R₁, R₂, R₃ and R₄independently of one another are alkyl, or R₁ and R₃ together arealkylene, or, independently of one another, R₁ and R₂, or R₃ and R₄,together are alkylene or azaalkylene, and R₅ is hydrogen, methyl orphenyl and Y is hydrogen, oxyl, alkyl, alkenyl, alkynyl, alkoxyalkyl,aralkyl, 2,3-epoxypropyl, an aliphatic acyl group or one of the groups--CH₂ COOR₆, --CH₂ --CH(R₇)--OR₈, --COOR₉ or --CONHR₉, in which R₆ isalkyl, alkenyl, phenyl, aralkyl or cycloalkyl and R₇ is hydrogen, methylor phenyl and R₈ is hydrogen or an aliphatic or aromatic or anaraliphatic or alicyclic acyl group, in which the aromatic part can beunsubstituted or substituted by chlorine, alkyl, alkoxy and/or hydroxyl,and R₉ is alkyl, cyclohexyl, phenyl or benzyl and R₁₀ is a trivalentorganic radical and R₁₁ is a divalent organic radical, R₁₀ and R₁₁completing the N-containing ring to give a 5-membered, 6-membered or7-membered ring, and r is 1 or 2 and equal to the number ofcoordinatively bonded phenolate anions in the molecule and B is a ligandhaving a single negative charge and s is an integer from 0 to 2, and thesum (q-s)/r+s must equal q, and m is an integer from 0 to 3, the sumt.[(p-s)/R]+s+m being equal to the coordination number of the metal ionM, and A is H₂ O or an amine of the formula III ##STR2## in which R₁₂ issubstituted or unsubstituted alkyl, cycloalkyl, aryl or aralkyl, asubstituted or unsubstituted aminoalkyl group or a piperidinyl group andR₁₃ is hydrogen or substituted or unsubstituted alkyl or cycloalkyl, asubstituted or unsubstituted aminoalkyl group or a piperidinyl group, orR₁₂ and R₁₃ together with the N atom form a pyrrolidine, piperidine ormorpholine ring which is substituted by alkyl groups or isunsubstituted, and R₁₄ is hydrogen or substituted or unsubstitutedalkyl.

As alkyl, R₁, R₂, R₃ and R₄ independently of one another are,especially, alkyl having 1-6 C atoms, preferably ethyl and veryparticularly methyl.

As alkylene, R₁ and R₃ together are, especially, alkylene having 1-6 Catoms, in particular methylene or ethylene.

R₁ and R₂, or R₃ and R₄, together as alkylene are especiallystraight-chain or branched alkylene having 4-8 C atoms, in particularpentamethylene, and as azaalkylene are, especially, straight-chain orbranched azaalkylene having 4-16, and in particular 4-10, C atoms, whichcan be substituted on the N atom, especially by a monovalent radical Yand in particular by alkyl, such as alkyl having 1-6 C atoms, especiallymethyl, but which, especially, is substituted on the N atom, such as3-aza-pentamethylene and especially2,2,4,4-tetramethyl-3-aza-pentamethylene,2,2,3,4,4-pentamethyl-3-aza-pentamethylene or the N-oxyl of2,2,4,4-tetramethyl-3-aza-pentamethylene. Preferably, only one of thepairs R₁ /R₂ and R₃ /R₄ is alkylene or azaalkylene and the other is ineach case alkyl, and in particular all of the radicals R₁, R₂, R₃ and R₄are alkyl. R₅ is especially hydrogen or methyl.

As alkyl, Y is especially alkyl having 1-12 C atoms, preferablyα-unbranched, and in particular having 1-4 C atoms, and veryparticularly is methyl.

As alkenyl, Y is especially alkenyl having 3-12, and in particularhaving 3-6, C atoms, such as allyl, methallyl, n-hex-3-enyl,n-oct-4-enyl and n-undec-10-enyl.

As alkynyl, Y is especially alkynyl having 3-6 C atoms, such aspropargyl, n-but-1-ynyl, but-2-ynyl and n-hex-1-ynyl.

If Y is alkoxyalkyl, the alkyl part can contain 1-3 C atoms and thealkoxy part can consist of 1-18 C atoms, as, for example, inmethoxymethyl, ethoxymethyl, 2-methoxyethyl, 2-ethoxyethyl,2-n-butoxyethyl, 3-n-butoxyethyl, 2-octoxyethyl or 2-octadecyloxyethyl.Compounds in which Y is an alkoxy group having 2-5 C atoms are to bementioned in particular.

As aralkyl, Y is aralkyl having 7-9 C atoms, for example benzyl orα-phenylethyl.

As an aliphatic acyl group, Y is especially an aliphatic acyl grouphaving 1-4 C atoms, for example formyl, acetyl, acryloyl or crotonyl,especially acetyl.

If Y is the group --CH₂ COOR₆, R₆ is C₁ -C₁₂ alkyl, for example methyl,ethyl, isopropyl, n-butyl, isobutyl, t-butyl, isopentyl, n-octyl,n-decyl or n-dodecyl; preferably, R₆ is C₁ -C₄ alkyl, or R₆ is C₃ -C₆alkenyl, for example allyl, 2-butenyl or 2-hexenyl, or C₇ -C₈ aralkyl,for example benzyl or α-phenylethyl, or, finally, C₅ -C₇ cycloalkyl,especially cyclohexyl.

If Y is the group --CH₂ --CH(R₇)--OR₈, R₇ is hydrogen, methyl or phenyl,especially hydrogen. As an aliphatic C₁ -C₁₈ acyl radical, R₈ is, forexample, formyl, acetyl, propionyl, butyryl, octanoyl, dodecanoyl,stearoyl or acryloyl. As an aromatic C₇ acyl radical, R₈ is benzoyl andas an araliphatic C₈ -C₉ acyl radical R₈ is cinnamoyl, phenylacetyl orphenylpropionyl. The aromatic part is unsubstituted or substituted bychlorine or C₁ -C₄ alkyl, such as methyl, ethyl, n-propyl or t-butyl, orby C₁ -C₈ alkoxy, such as methoxy, ethoxy, butoxy or octoxy, and/orhydroxyl. Substituted aromatic acyl groups are, for example,chlorobenzoyl, toluoyl, isopropylbenzoyl, 2,4-dichlorobenzoyl,4-methoxybenzoyl, 3-butoxybenzoyl, 2-hydroxybenzoyl or3,5-di-t.-butyl-4-hydroxybenzoyl. An araliphatic substituted acyl groupis, for example, β-(3,5-di-t.-butyl-4-hydroxyphenyl)-propionyl. If R₈ isan alicyclic C₆ -C₉ acyl group, this can be cyclohexylcarbonyl or2,4-dimethylcyclohexylcarbonyl. Hydrogen is also a preferred meaning ofR.sub. 8.

If Y is the group --COOR₉, R₉ is C₁ -C₁₂ alkyl, for example methyl,ethyl, isobutyl, t-butyl, n-hexyl, n-octyl, n-decyl or n-dodecyl. Alkylgroups having 1-4 C atoms are preferred as R₉.

If Y is --CONHR₉, R₉ is especially cyclohexyl or phenyl.

IF A is an amine of the formula III, the substituents R₁₂, R₁₃ and R₁₄therein are, for example, C₁ -C₁₈ alkyl, such as methyl, ethyl,isopropyl, sec.-butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl orn-octadecyl, and preferably C₁ -C₈ alkyl.

If the alkyl is substituted alkyl, this is intended to signify,especially, C₁ -C₁₈ hydroxyalkyl, such as 1-hydroxyethyl,1-hydroxypropyl, 1-hydroxy-1-methyl-ethyl, 3-hydroxypentyl or1-hydroxy-2-methyl-ethyl, and preferably C₁ -C₆ hydroxyalkyl.

R₁₂ and R₁₃ can also be C₅ -C₁₂ cycloalkyl, which can be, for example,cyclopentyl, cyclohexyl, 4-methylcyclohexyl or 4-tert.-butylcyclohexyl.R₁₂ can also be C₆ -C₁₈ aryl, which can be, for example, phenyl, tolyl,xylyl, tert.-butylphenyl or dodecylphenyl. As aralkyl, R₁₂ can be C₇-C₂₀ aralkyl and is, for example, benzyl, 4-methylbenzyl,4-t.-butylbenzyl or 4-dodecylbenzyl, especially benzyl.

If R₁₂ and R₁₃ are a substituted or unsubstituted aminoalkyl group, thisis, especially, an aminoalkyl group substituted by a piperidinyl group,for example an aminoalkyl group of the formula IIc ##STR3## in which R₁,R₂, R₃, R₄, R₁₀ and Y are as defined above and v is an integer from 1 to8.

If R₁₂ and R₁₃ are a piperidinyl group, this is preferably a piperidinylgroup of the formula (IIa), in which R₁₀ is a trivalent radical ##STR4##

R₁₂ and R₁₃, together with the N atom of the ligand A, can form apyrrolidine, piperidine or morpholine ring which is substituted by alkylgroups or is unsubstituted. In this case, the ring can be, for example,a 2,5-dimethylpyrrolidine, 4-methylpiperidine,2,2,6,6-tetramethylpiperidine, 2,6-dimethylmorpholine, pyrrolidine,piperidine or morpholine ring, especially a2,2,6,6-tetramethylpiperidine ring.

Thus, according to the definition, the ligand A is a primary, secondaryor tertiary amine which is able to form a complex with the metalchelates indicated above. Examples of such amines are: n-butylamine,n-dodecylamine, β-ethylhexylamine, benzylamine, 4-octylbenzylamine,dibutylamine, dicyclohexylamine, dioctadecylamine, morpholine,2,2,6,6-tetramethylpiperidine, N-ethylaniline, tri-n-octylamine,N,N-dimethylaniline, N,N-dimethyl-cyclohexylamine, N-ethylpiperidine,N-methylpyrrolidine, dibenzylpropylamine,N-benzyl-2,5-dimethylpyrrolidine,4-dimethylamino-2,2,6,6-tetramethylpiperidine,4-dimethylamino-1,2,2,6,6-pentamethylpiperidine,N,N'-methyl-N,N'-(1,2,2,6,6-pentamethyl-4-piperidyl)-ethylenediamine,hydroxyethylamine, di-(hydroxyethyl)amine, tri-(hydroxyethyl)-amine,tri-(2-hydroxy-propyl)-amine, N-phenyl-N,N-di-(hydroxyethyl)-amine orhydroxypropyl-amine.

The complexes, according to the invention, of the formula I contain, permol of metal M^(q+), 0 to 3 mols of the amine ligand A, which can beentirely or partly replaced by water. The molar proportion expressed bym in the formula I is thus made up of the sum of m' mols of amine ligandand m" mols of water; the molar proportions expressed by m' and m" donot need to be an integer. Preferred complexes are those which have alow water content, since these dissolve in nonpolar polymers better thando more highly hydrated complexes. m' thus assumes approximately thevalue of m.

A cation M of the valency q is, for example, a cation of the seriesMg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Zn²⁺, Cd²⁺, Al³⁺, Sn²⁺, Cr³⁺, Co²⁺ and Ni²⁺, anoxo complex of metal ions, especially VO²⁺ and MoO₂ ²⁺, or a tin-alkylion of the formula (R*)₂ Sn²⁺ or (CH₂ CH₂ COOR*)₂ Sn²⁺, in which R* isC₁ -C₈ alkyl, but especially ethyl, n-propyl or n-octyl and inparticular n-butyl, especially Ca²⁺, Mg²⁺, Zn²⁺, Co²⁺ and in particularNi²⁺ or Al³⁺. The coordination numbers of these cations are known tothose skilled in the art and are 4 or 6, depending on the metal.

q is 2 or 3, especially 2.

r is 1 or 2 and corresponds to the number of phenolate anions in theligand L. Thus, if a ligand molecule contains several phenolic --OHgroups, whether or not all of the phenolic OH groups are deprotonated,and thus contribute to the total charge r⁻ on the ligand L, depends onthe corresponding stability constants and the ratio M/1.

t indicates the detentation of the ligand L as 2, 3 and 4, i.e. tdescribes the number of donor atoms in the molecule which enter intodirect interaction with the metal centre M^(q+). 2-, 3- or 4-dentateligands can be used for the set object and the metal complexes formedare uncharged.

The chelate-forming agent L must meet the condition that it contains atleast one of the groups IIa or IIb. The meaning of the symbols R₁₀ andR₁₁ is then such that the groups IIa and IIb are, for example,derivatives of pyrrolidine, imidazolidine, 1,4-diazacycloheptanone,piperazine, 1-aza-4-thiacyclohexane or dipiperidyl and in particular ofpiperidine. Amongst the numerous piperidines, those to be mentioned arenot only the simple piperidines substituted in the 4-position, but alsospiro compounds, such as 1-oxa-3,8-diaza-spiro[4,5]-decanes(piperidine-spirooxazolidines), 1-oxa-6-aza-spiro[2,5]-octanes(piperidine-spiro-oxiranes), 1,4-dioxa-8-aza-spiro[4,5]-decane and1,5-dioxa-9-azaspiro[5,5]-undecane, and also the analogous 1-thia and4-aza compounds of the two last-mentioned piperidine-spiro-ketals, andin particular 1,3,8-triazaspiro[4,5]-decanes(piperidine-spirohydantoins).

Metal complexes which have proved particularly suitable are those of theformula I in which L^(r+) is a 2-, 3- or 4-dentate chelate-forming agentselected from the category consisting of the groups IVa, IVb and IVc##STR5## in which u is 0, 1 or 2 and r is as defined above and R₁₅ andR₁₆ independently of one another are hydrogen, C₁ -C₁₈ alkyl, which canbe unsubstituted or substituted by a group Va, Vb or Vc: ##STR6## or agroup Vc, or a group of the formula VI ##STR7## in the p-position,halogen or a radical --OR₂₄, or R₁₅ and R₁₆ together are a1,3-butadiene-1,4-diyl radical, and R₅ and Y are as defined and X₁ andX₂ independently of one another are --O-- or ##STR8## and R₂₁ ishydrogen or C₁ -C₈ alkyl and R₂₂ is hydrogen or a group --X₁ R₂₆, inwhich X₁ is as defined above, and Z is --O-- or ##STR9## and R₂₃ is C₁-C₁₈ alkyl, C₃ -C₆ alkenyl, C₃ -C₄ alkynyl, C₅ -C₇ cycloalkyl, C₆ -C₁₀aryl, C₇ -C₁₄ aralkyl, C₇ -C₁₄ alkylphenyl or a group of the formula VI,and R₂₄ is hydrogen or C₁ -C₈ alkyl, C₅ -C₇ cycloalkyl, C₆ -C₁₄ aryl, C₇-C₁₄ aralkyl or C₂ -C₁₂ alkenyl which are unsubstituted or substitutedby a group of the formula Vc; or R₂₄ is an aliphatic C₁ -C₁₈ acyl group,aromatic C₇ acyl group, araliphatic C₈ -C₉ acyl group or alicyclic C₆-C₉ acyl group, which is unsubstituted or substituted by chlorine, C₁-C₈ alkyl, C₁ -C₈ alkoxy, a group Vc and/or hydroxyl, and R₂₅ ishydrogen, C₁ -C₁₈ alkyl, which can be unsubstituted or substituted by agroup of the formula Vc, or C₃ -C₆ alkenyl, C₃ -C₆ alkenyl, C₃ -C₄alkynyl, C₅ -C₇ cycloalkyl, C₆ -C₁₀ aryl, C₇ -C₁₄ aralkyl, a group ofthe formula CH₂ --CH(R₅)--OR₂₆ or a group of the formula VI, and R₂₆ ishydrogen, C₁ -C₁₈ alkyl, C₃ -C₆ alkenyl, cyclohexyl, benzyl or analiphatic C₁ -C₁₈ acyl group, aromatic C₇ acyl group, araliphatic C₈ -C₉acyl group alicyclic C₆ -C₉ acyl group, which is unsubstituted orsubstituted by chlorine, C₁ -C₈ alkyl, C₁ -C₈ alkoxy and/or hydroxyl,and R₁₇ is hydrogen, C₁ -C₁₈ alkyl, halogen, a group --OR₂₄ or a groupof the formula Vc and R₁₈ is a group --N(R₂₅)R₂₇ and R₁₉ is hydrogen, orR₁₈ and R₁₉ together are ═O or ═NR₂₇, and R₂₀ is hydrogen, C₇ -C₁₄aralkyl, C₇ -C₁₄ alkylphenyl, or C₁ -C₁₈ alkyl, C₂ -C₁₂ alkenyl, C₅ -C₁₂cycloalkyl or C₆ -C₁₄ aryl, which are unsubstiuted or substituted by agroup of the formula Vc, or, if R₁₈ and R₁₉ together are ═O, R₂₀ is agroup of the formula Va; or R₂₀ is also a group of the formula VII##STR10## in which R₁₅, R₁₆, R₁₈ and R₁₉ are as defined above and R₂₈ isC₁ -C₁₂ alkylene, butenylene, C₆ -C₁₀ arylene or diphenylene, and R₂₇ ishydrogen, C₇ -C₁₄ aralkyl, C₇ -C₁₄ alkylphenyl, hydroxyl, or C₁ -C₁₈alkyl, C₂ -C₁₂ alkenyl, C₅ -C₁₂ cycloalkyl or C₆ -C₁₄ aryl, which areunsubstituted or substituted by a group of the formula Vc, or a group ofthe formula VI, or a group of the formula --CH₂ --CH(R₅)--OR₂₆ ; or R₂₇is also a group of the formulae VIIIa or VIIIb ##STR11## in which R₂₀ 'has the meaning defined for R₂₀ with the exception of the groups of theformula VII, and R₁₅, R₁₆, R₂₅ and R₂₈ are as defined above.

The substituents mentioned in the above formulae IVa, IVb, IVc, Va, Vb,Vc, VI, VII, VIIIa and VIIIb are, for example, as defined below:

R₅ and Y are as defined above.

u is 0, 1 or 2, especially 0.

If R₁₅ and R₁₆ independently of one another are C₁ -C₁₈ alkyl, this canbe, for example, methyl, ethyl, iso-propyl, n-butyl, t-butyl, amyl,n-hexyl, n-octyl, t-octyl, n-decyl, n-dodecyl, n-octadecyl or2-ethyl-hexyl. Preferred alkyl groups are those having 1-5 C atoms. Thealkyl groups can be substituted by a group of the formulae Va, Vb or Vc,preferably Va or Vc; in this case alkyl groups having 1-4 C atoms arepreferred. Preferred compounds of the formula I are those in which atmost one of the radicals R₁₅ and R₁₆ is substituted by a group of theformula Va, Vb or Vc. The radicals R₁₅ or R₁₆ can also be a group Vc.

One of the radicals R₁₅ and R₁₆ can also be a group of the formula VI.For reasons of synthesis, this group must be in the p-position relativeto the phenolate oxygen.

If R₁₅ and R₁₆ are halogen, this can be chlorine or bromine, especiallychlorine.

R₁₅ and R₁₆ are preferably also hydrogen or --OR₂₄.

As C₁ -C₁₈ alkyl, R₁₇ is, for example, methyl, ethyl, propyl, butyl,n-hexyl, n-octyl, n-decyl, n-dodecyl or n-octadecyl, and alkyl groupshaving 1-12 C atoms are preferred.

As halogen, R₁₇ is especially chlorine.

Compounds in which R₁₇ is hydrogen, --OR₂₄ and especially a group of theformula Vc are also preferred.

If R₂₀ and R₂₇ are C₇ -C₁₄ aralkyl, this can be, for example, benzyl,α-phenylethyl or 2-phenylpropyl, especially benzyl.

If R₂₀, R₂₄, R₂₅ and R₂₇ are C₁ -C₁₈ alkyl, this signifies, for example,methyl, ethyl, isio-propyl, n-butyl, t-butyl, amyl, n-hexyl, n-octyl,t-octyl, n-decyl, n-dodecyl or n-octadecyl. Amongst these groups, alkylgroups having 1-12 C atoms are preferred. Further preferred alkyl groupsare those which are substituted by a group of the formula Vc, andamongst these, in particular, those having 1-4 C atoms.

As C₂ -C₁₂ alkenyl, R₂₀, R₂₄ and R₂₇ are, for example, allyl, methally,n-hex-3-enyl, n-oct-4-enyl or n-undec-1-enyl. Alkenyl groups having 2-6C atoms are preferred and these can be unsubstituted or substituted by agroup of the formula Vc.

R₂₀ and R₂₇ can also be C₅ -C₁₂ cycloalkyl. This is then, for example,cyclopentyl, cyclohexyl, methylcyclohexyl, cyclooctyl,dimethylcyclohexyl, propylcyclohexyl or dehydronaphthyl-α-methyl;especially cyclohexyl. If R₂₀ and R₂₇ are cycloalkyl, they arepreferably substituted by a group of the formula Vc.

If R₂₀, R₂₄ and R₂₇ are C₆ -C₁₄ aryl, this is intended to signify, forexample, alkylphenyl having 1-8 C atoms, and especially having 1-4 Catoms, in the alkyl part, but especially phenyl. The aryl ring ispreferably substituted by a group of the formula Vc.

Further preferred compounds are those in which one of R₂₀ and R₂₇ ishydrogen.

R₂₇ can preferably be a group of the formula VI.

As C₁ -C₈ alkyl, R₂₁ is, for example, methyl, ethyl, iso-propyl,n-butyl, amyl, n-hexyl or n-octyl. Alkyl groups having 1-4 C atoms arepreferred, but in particular R₂₁ is methyl or hydrogen.

As C₁ -C₁₈ alkyl, R₂₃ an R₂₆ are, for example, methyl, ethyl,iso-propyl, n-butyl, t-butyl, amyl, n-hexyl, n-octyl, t-ocyl, n-decyl,n-dodecyl or n-octadecyl.

As C₃ -C₆ alkenyl, R₂₃, R₂₅ and R₂₆ are, for example, allyl, methallyl,but-2-enyl or hex-3-enyl, especially allyl.

If R₂₃ and R₂₅ are C₃ -C₄ alkynyl, this is especially propargyl.

As C₅ -C₇ cycloalkyl, R₂₃, R₂₄ and R₂₅ are, for example, cyclopentyl,cyclohexyl or methylcyclohexyl, especially cyclohexyl.

As C₆ -C₁₀ aryl, R₂₃ and R₂₅ are, for example, phenyl, α-naphthyl orβ-naphthyl, especially phenyl.

If R₂₃ and R₂₅ are C₇ -C₁₄ aralkyl, this is, for example, benzyl,α-phenylethyl or 2-phenylethyl, especially benzyl.

As C₇ -C₁₄ alkylphenyl, R₂₃ is, for example 4-t-butylphenyl or4-methylphenyl.

R₂₃ is, mreover, preferably also a group of the formula VI.

As C₇ -C₁₄ aralkyl, R₂₄ is, for example, benzyl, α-phenylethyl or2-phenylpropyl, especially benzyl. The aryl radical is preferablysubstituted by a group of the formula Vc.

As an aliphatic C₁ -C₁₈ acyl radical, R₂₄ and R₂₆ are, for example,formyl, acetyl, propionyl, butyryl, octanoyl, dodecanoyl, stearoyl oracryloyl. As an aromatic C₇ acyl radical, R₂₄ and R₂₆ are benzoyl and asan araliphatic C₈ -C₉ acyl radical R₂₄ and R₂₆ are cinnamoyl,phenylacetyl or phenylpropionyl. The aromatic part is unsubstituted orsubstituted by chlorine or C₁ -C₄ alkyl, such as methyl, ethyl, n-propylor t-butyl, or by C₁ -C₈ alkoxy, such as methoxy, ethoxy, butoxy oroctoxy, and/or hydroxyl. Substituted aromatic acyl groups are, forexample, chlorobenzoyl, toluoyl, isopropylbenzoyl, 2,4-dichlorobenzoyl,4-methoxybenzoyl, 3-butoxybenzoyl, 2-hydroxybenzoyl or3,5-di-t.-butyl-4-hydroxy-benzoyl. An araliphatic substituted acyl groupis, for example, β-(3,5-di-t.-butyl-4-hydroxyphenyl)-propionyl. If R₂₄and R₂₆ are alicyclic C₆ -C₉ acyl groups, these can becyclohexylcarbonyl or 2,4-dimethylcyclohexylcarbonyl.

A preferred meaning of R₂₅ is also a group --CH₂ --CH(R₅) --OR₁₆.

As C₁ -C₁₂ alkylene, R₂₈ can be, for example, methylene, dimethylene,trimethylene, tetramethylene, hexamethylene, octamethylene,decamethylene or dodecamethylene.

As C₆ -C₁₀ arylene, R₂₈ is, for example, phenylene or naphthylene.

Although compounds of the formula I which contain up to 4 groups of theformula Va, Vb or VI in the ligand L can certainly also be usedindustrially, those compounds containing 1 or 2 of the said groups arepreferred for practical reasons. Further nitrogen heterocyclic compoundscan, however, occur in the amine ligand A.

Amongst the groups Va, Vb and VI occurring in the molecule, those of theformula Va and VI are preferred in particular.

X₁ in formula Va is preferably ##STR12## and X₂ in formula Vc isespecially --O--.

As an anion having a single charge, B is, for example, an anion of analiphatic or aromatic carboxylic acid, of a phosphonic acid half-ester,of a phosphinic acid, of a phosphinous acid or of an enol of the formulaIX ##STR13## in which R₂₉ is alkyl, alkenyl, cycloalkyl, aralkyl or aryland R₃₀ is hydrogen, alkyl, alkenyl, cycloalkyl, aralkyl, aryl oralkoxycarbonyl, or R₂₉ and R₃₀ together are subsituted or unsubstituted1,4-butadi-1,3-enylene or 1,4-butylene, and R₃₁ is substituted orunsubsituted alkyl, alkenyl, cycloalkyl, aralkyl, aryl or alkoxy, orsubstituted or unsubstituted amino, and R₃₂ is oxo or substituted orunsubstituted imino.

An anion B, having a signle charge, of an aliphatic carboxylic acid isespecially an anion of a carboxylic acid R₃₃ -COOH, in which R₃₃ is asubstituted or unsubsituted aliphatic hydrocarbon radical, which isespecially alkyl having 1-25, and in particular 1-12, C atoms,cycloalkyl having 5-12, and especially 5-6, C atoms, or alkenyl having2-25, and especially 2-12, C atoms and in particular vinyl, theseradicals being unsubstituted or substituted by halogen, especiallychlorine, hydroxyl, alkyl having 1-6 C atoms or alkoxy having 1-6 Catoms.

Examples of R₃₃ are methyl, ethyl, n-hexyl, n-undecyl, 1-ethyl-n-pentyl,cyclopentyl, cyclohexyl, vinyl, allyl or crotonyl or 4-chlorobutyl.

An anion B, having a single charge, of an aliphatic carboxylic acid isalso an anion of an aliphatic α- or β-aminocarboxylic acid, especiallyof such an acid having 2-20, and in particular 2-12 C atoms, which isunsubstituted on the amino group but preferably is monoalkylated ordialkylated on the amino group, such as by branched or, especially,straight-chain alkyl having 1-12 and in particular 1-8 C atoms. Examplesof α-aminocarboxylic acids are glycine, α-alanine, valine andisoleucine, which are monosubstituted or disubstituted on the aminogroup, especially by n-alkyl having 1-8 C atoms, such asdi-n-octyl-glycine. An example of β-aminoccarboxylic acids is β-alaninewhich is monosubstituted or disubstituted on the amino group, especiallyby n-alkyl having 1-8 C atoms, such as di-n-propyl-β-alanine.

An anion B, having a single charge, of an aromatic carboxylic acid isespecially an anion of a carboxylic acid R₃₄ -COOH, in which R₃₄ is asubstituted or unsubstituted aromatic hydrocarbon radical, which isespecially aryl having 6-10 C atoms or aralkyl having 7-14 C atoms. Theradical can be, in particular, phenyl, benzyl or phenylethyl and thesecan be unsubstituted in the aryl part. Substituents in the aryl partare, especially, hydroxyl, cyclohexyl, phenyl, benzyl, α,α-dimethylbenzyl and especially C₁ -C₁₂ alkyl, such as methyl, ethyl,iso-propyl, t.-butyl, t-octyl or n-dodecyl, especially t-butyl.Therefore, R₃₄ can be, for example,3,5-di-t.-butyl-4-hydroxyphenyl-ethyl, 3,5-di-t.-butyl-4-hydroxybenzylor 3,5-di-t.-butyl-4-hydroxybenzyl or 3,5-di-t.-butyl-4-hydroxyophenyl.

An anion B, having a single charge, of a phosphonic acid half-ester orof a phosphinic acid is, especially, an anion of a phosphonic acidhalf-ester or of a phosphinic acid of the formulae X, XI or XII##STR14## in which R₃₅ is C₁ -C₁₈ alkyl and R₃₆ is C₁ -C₈ alkyl,cyclohexyl, or C₇ -C₁₁ aralkyl or phenyl which are unsubstituted ormonosubstituted by chlorine, C₁ -C₄ alkyl or methoxy, or C₁ -C₄ alkoxy,benzyloxy, phenoxy or tolyloxy and R₃₇ and R₃₈ independently of oneanother are hydrogen, C₁ -C₈ alkyl, cyclohexyl, or C₇ -C₁₁ aralkyl orphenyl which are unsubstituted or monosubstituted or disubstituted bychlorine, C₁ -C₄ alkyl and/or C₁ -C₄ alkoxy, or R₃₇ and R₃₈ togetherwith the N atom to which they are bonded form a pyrrolidine, piperidineor morpholine ring, and R₃₉ is hydrogen, C₁ -C₆ alkyl, phenyl or4-methoxyphenyl and R₄₀ is hydrogen or methyl and R₄₁ and R₄₂independently of one another are C₁ -C₁₂ alkyl.

As C₁ -C₁₈ alkyl, R₃₅ is, for example, methyl, ethyl, propyl, n-butyl,n-hexyl, n-octyl, n-dodecyl, or n-octadecyl, and especially C₁ -C₄alkyl.

As C₁ -C₈ alkyl, R₃₆, R₃₇ and R₃₈ are, for example, linear or branchedalkyl groups, such as methyl, ethyl, propyl, isopropyl, n-butyl,n-hexyl, n-octyl or 2-ethylhexyl; C₁ -C₄ alkyl groups are preferred.

As C₇ -C₁₁ aralkyl, which can be substituted or unsubstituted, R₃₆, R₃₇and R₃₈ are, for example, benzyl, 4-methylbenzyl, 4-isopropylbenzyl,3-chlorobenzyl, 4-methoxybenzyl or phenylethyl, especially benzyl.

As phenyl, which can be substituted or unsubstituted, R₃₆, R₃₇ and R₃₈are, for example, phenyl, 4-methylphenyl, 3-chlorophenyl,4-methoxyphenyl or 4-butoxyphenyl, especially phenyl.

As C₁ -C₄ alkoxy, R₃₆ is, for example, methoxy, ethoxy, propoxy orbutoxy.

R₃₇ and R₃₈, together with the nitrogen atom to which they are bonded,can also form a pyrrolidine, piperidine or morpholine ring, especially apiperidine or morpholine ring.

As C₁ -C₆ alkyl, R₃₉ is, for example, methyl, ethyl, propyl, n-butyl orn-hexyl, especially methyl.

A further preferred meaning of R₃₉ is hydrogen.

As C₁ -C₁₂ alkyl, R₄₁ and R₄₂ independently of one another are, forexample, methyl, ethyl, ispropyl, t-butyl, amyl, hexyl, t-octyl orn-dodecyl. Alkyl groups having 1-4 C atoms, especially t-butyl, arepreferred.

An anion B, having a single charge, of a phosphinous acid is especiallyan anion of a phosphinous acid of the formula ##STR15## in which R₄₃ andR₄₄ independently of one another are alkyl, or phenyl, benzyl orcyclohexyl which are unsubstituted or substituted by chlorine, alkyland/or alkoxy.

If R₄₃ and R₄₄ independently of one another are alkyl, this isespecially alkyl having 1-18 C atoms, such as methyl, ethyl, n-butyl,n-hexyl, n-octyl, n-dodecyl or n-octadecyl.

If R₄₃ and R₄₄ independently of one another are phenyl, benzyl orcyclohexyl, these can be unsubstituted or monosubstituted ordisubstituted by chlorine, C₁ -C₄ alkyl and/or C₁ -C₄ alkoxy. Possibleradicals are 4-methoxyphenyl, 3-chlorobenzyl, 4-butylphenyl,4-methylcyclohexyl or 3-chloro-4-methylphenyl.

If B, as an anion having a single charge, is an enol of the formula IX,R₂₉, R₃₀ and R₃₁, as alkyl, are especially alkyl having 1-12 C atoms andin particular having 1-6 C atoms, such as methyl, ethyl, n-propyl,n-butyl or n-hexyl.

As alkenyl, R₂₉, R₃₀ and R₃₁ are especially alkenyl having 2-12 C atomsand in particular 2-6 C atoms, such as allyl, methallyl or n-hex-3-enyl.

As cycloalkyl, R₂₉, R₃₀ and R₃₁ are especially cycloalkyl having 5-12and in particular 5-6 C atoms, such as cyclohexyl.

As aralkyl, R₂₉, R₃₀ and R₃₁ are especially aralkyl having 7-12 C atoms,such as benzyl or phenylethyl.

As aryl, R₂₉, R₃₀ and R₃₁ are especially aryl having 6-10 C atoms, suchas phenyl, naphthyl or phenyl substituted by alkyl having 1-12 andespecially 1-4 C atoms, such as methyl, ethyl or butyl; by alkoxy having1-12 and especially 1-4 C atoms, such as methoxy or butoxy, or byhalogen, such as chlorine.

As alkoxycarbonyl, R₃₀ is especially alkoxycarbonyl having 2-12 and inparticular 2-6 C atoms, such as methoxycarbonyl or ethoxycarbonyl.

Substituted or unsubstituted 1,4-butadi-1,3-enylene as R₂₉ and R₃₀ isespecially unsubstituted 1,4-butadi-1,3-enylene, or1,4-butadi-1,3-enylene which carries as a substituent, for example, C₁-C₁₂ alkyl, especially C₁ -C₆ alkyl, such as methyl; C₁ -C₁₂ alkoxy,especially C₁ -C₄ alkoxy, such as n-butoxy; or halogen, such aschlorine.

As substituted alkyl, R₃₁ is especially alkyl having 1-12 and inparticular 1-6 C atoms which carries halogen, such as chlorine, assubstituents.

If R₃₁ is alkoxy, it is especially alkoxy having 1-12, and in particular1-6, C atoms, such as methoxy or ethoxy.

R₃₁ can be an amino group; if this is substituted it is especiallyalkylamino having 1-12 C atoms, such as methylamino, dialkylamino having2-24 C atoms, such as dimethylamino, and especially anilino, the phenylring of which is unsubstituted or carries alkyl having 1-6 C atoms, suchas methyl, or especially alkoxy having 1-6 C atoms, such as methoxy, assubstituents in the p-position, m-position or, especially, o-position.

Preferred anions B having a single charge are, in particular, those ofan aliphatic or aromatic carboxylic acid, of a phosphonic acid or of anenol of the formula IX.

s is 0 to 2 and is preferably 0.

Preferred metal complexes are those of the formula XIV

    [M.sup.q⊕ ][L.sub.1.sup.r⊖ ].sub.q/r ·mA (XIV)

in which M is Mg²⁺, VO²⁺, Ca²⁺, Mn²⁺, Zn²⁺, Co²⁺, Ni²⁺ or Al³⁺ and q is2 or 3 and L₁ is a t-dentate group of the formula IVa which issubstituted by at least one group of the formulae Va, Vb or VI, and u is0, 1 or 2 and t is 3, and R₁₅ and R₁₆ independently of one another arehydrogen or C₁ -C₁₈ alkyl which can be unsubstituted or substituted by agroup of the formulae Va, Vb or Vc; or a group Vc, or a group of theformula VI in the p-position, halogen or a radical --OR₂₄, or R₁₅ andR₁₆ together form a 1,3-butadiene-1,4-diyl radical, and R₅ is hydrogen,methyl or phenyl and Y is hydrogen, oxyl, C₁ -C₁₂ alkyl, C₃ -C₁₂alkenyl, C₃ -C₆ alkynyl, C₂ -C₂₁ alkoxyalkyl, C₇ -C₉ aralkyl,2,3-epoxypropyl, an aliphatic C₁ -C₄ acyl group or one of the groups--CH₂ COOR₆, --CH₂ --CH(R₇)--OR₈, --COOR₉ or --CONHR₉, in which R₆ is C₁-C₁₂ alkyl, C₃ -C₆ alkenyl, phenyl, C₇ -C₈ aralkyl or cyclohexyl and R₇is hydrogen, methyl or phenyl and R₈ is hydrogen, an aliphatic C₁ -C₁₈acyl group or an aromatic C₇ acyl group, an araliphatic C₈ -C₉ acylgroup or an alicyclic C₆ -C₉ acyl group, in which the aromatic part canbe unsubstituted or substituted by chlorine, C₁ -C₄ alkyl, C₁ -C₈ alkoxyand/or hydroxyl, and R₉ is C₁ -C₁₂ alkyl, cyclohexyl, phenyl or benzyl,and X₁ and X₂ independently of one another are --O-- or ##STR16## andR₂₁ is hydrogen or C₁ -C₈ alkyl and R₂₂ is hydrogen or a group --X₁ R₂₆and Z is --O-- or ##STR17## and R₂₃ is C₁ -C₁₈ alkyl, C₃ -C₆ alkenyl, C₃-C₄ alkynyl, C₅ -C₇ cycloalkyl, C₆ -C₁₀ aryl, C₇ -C₁₄ aralkyl, C₇ -C₁₄alkylphenyl or a group of the formula VI, in which Y and R₂₁ are asdefined, and R₂₄ is hydrogen or C₁ -C₈ alkyl, C₅ -C₇ cycloalkyl, C₆ -C₁₄aryl, C₇ -C₁₄ aralkyl or C₂ -C₁₂ alkenyl which are unsubstituted orsubstituted by a group of the formula Vc, in which X₂ and R₂₃ are asdefined, or is an aliphatic C₁ -C₁₈ acyl group, aromatic C₇ acyl group,araliphatic C₈ -C₉ acyl group or alicyclic C₆ -C₉ acyl group which isunsubstituted or substituted by chlorine, C₁ -C₈ alkyl, C₁ -C₈ alkoxy, agroup Vc and/or hydroxyl, and R₂₅ is hydrogen, C₁ -C₁₈ alkyl, which canbe unsubstituted or substituted by a group of the formula Vc, in whichX₂ and R₂₃ are as defined, or C₃ -C₆ alkenyl, C₃ -C₄ alkynyl, C₅ -C₇cycloalkyl, C₆ -C₁₀ aryl, C₇ -C₁₄ aralkyl, a group of the formula CH₂--CH(R₅)--OR₂₆ or a group of the formula VI, and R₂₆ is hydrogen, C₁-C₁₈ alkyl, C₃ -C₆ alkenyl, cyclohexyl, benzyl or an aliphatic C₁ -C₁₈acyl group, aromatic C₇ acyl group, araliphatic C₈ -C₉ acyl group oralicyclic C₆ -C₉ acyl group which is unsubstituted or substituted bychlorine, C₁ -C₈ alkyl, C₁ -C₈ alkoxy and/or hydroxyl, and r is 1 or 2and m is a number from 0 to 3, the sum (3·q/r)+m being equal to thecoordination number of the metal ion M, and A is H₂ O or an amine of theformula III, in which R₁₂ is unsubstituted or --OH-- substituted C₁ -C₁₈alkyl, C₅ -C₁₂ cycloalkyl, C₆ -C₁₈ aryl, C₇ -C₂₀ aralkyl, a substitutedor unsubstituted aminoalkyl group or a piperidinyl group, and R₁₃ ishydrogen or unsubstituted or --OH-substituted C₁ -C₁₈ alkyl, C₅ -C₁₂cycloalkyl, a substituted or unsubstituted aminoalkyl group or apiperidinyl group, or R₁₂ and R₁₃ together with the N atom form apyrrolidine, piperidine or morpholine ring which is substituted by alkylgroups or is unsubstituted, and R₁₄ is hydrogen or unsubstituted or--OH-substituted C₁ -C₁₈ alkyl.

Amongst the compounds of the formula XIV, those to be mentioned inparticular are those in which M is Ca²⁺, Mn²⁺, Zn²⁺, Co²⁺, Ni²⁺ or Al³⁺and q is 2 or 3 and u is 0 and L₁ and t are as defined above, and R₁₅and R₁₆ independently of one another are hydrogen or C₁ -C₈ alkyl whichcan be unsubstituted or substituted by a group of the formulae Va, Vb orVc; or a group Vc or a radical --OR₂₄, and R₅ is hydrogen or methyl andY is hydrogen, C₁ -C₄ alkyl, C₃ -C₆ alkenyl, propargyl, C₂ -C₅alkoxyalkyl, benzyl, acetyl or one of the groups --CH₂ COOR₆, --CH₂CH(R₇)--OR₈, --COOR₉ or --CONHR₉, in which R₆ is C₁ -C₄ alkyl and R.sub.7 is hydrogen or methyl and R₈ is hydrogen and R₉ is C₁ -C₄ alkyl, andX₁ and X₂ independently of one another are --O-- or ##STR18## and R₂₁ ishydrogen or C₁ -C₄ alkyl and R₂₂ and Z are as defined above, and R₂₃ isC₁ -C₁₈ alkyl, allyl, propargyl, cyclohexyl, phenyl, 4-t-butylphenyl ora group of the formula VI, in which Y and R₂₁ are as defined, and R₂₄ ishydrogen or C₁ -C₁₂ alkyl, C₂ -C₆ alkenyl, cyclohexyl, phenyl or benzylwhich are unsubstituted or substituted by a group of the formula Vc, inwhich X₂ and R₂₃ are as defined, and R₂₅ is hydrogen, C₁ -C₁₂ alkyl,which can be unsubstituted or substituted by a group of the formula Vc,in which X₂ and R₂₃ are as defined, or allyl, propargyl, cyclohexyl,phenyl, benzyl or a group --CH₂ --CH(R₅)--OH, in which R₅ is as defined,and r and m and also the sum (3·q/r)+m are as defined above, and A is H₂O or an amine of the formula III, in which R₁₂ and R₁₃ independently ofone another are C₁ -C₈ alkyl, C₁ -C₆ hydroxyalkyl or a substitutedaminoalkyl group of the formula IId ##STR19## in which v is 1 to 8 andY, R₅ and R₂₁ are as defined, or R₁₂ and R₁₃ together form a piperidinegroup, and R₁₄ is hydrogen or C₁ -C₈ alkyl or C₁ -C₆ hydroxyalkyl.

Particularly preferred compounds of the formula XIV are those in which Mis Ca²⁺, Zn²⁺ or Ni²⁺ and q is 2 and u is 0 and L₁ is a t-dentate groupof the formula IVa, which is substituted by at least one group of theformulae Va or VI, and t is 2, and R₁₅ is --OR₂₄, C₁ -C₄ alkylsubstituted by a group Va or Vc, or a group Vc and R₁₆ is hydrogen or C₁-C₈ alkyl, and R₅ is hydrogen or methyl and Y is hydrogen, methyl oracetyl and X₁ is ##STR20## and X₂ is --O-- and R₂₁ is hydrogen or methyland R₂₃ is a group of the formula VI, and R₂₄ is C₁ -C₄ alkylsubstituted by a group of the formula Vc, in which X₂ and R₂₃ are asdefined, and R₂₅ is hydrogen, C₁ -C₁₂ alkyl, cyclohexyl, benzyl, phenylor a group of the formula --CH₂ --CH(R₅)--OH, and r is 1 and m is 0.

Compounds of very particular interest are those of the formula XIV inwhich R₁₅ is a C₁ -C₄ alkyl group which is substituted by a group of theformula Va and is in the o-position and R₁₆ is a1,1,3,3-tetramethylbutyl group in the p-position.

Examples of compounds of the formula XIV are: the 1:2 Ni²⁺ complex ofdi-{2-hydroxy-5-t-octyl-3-[N-methyl-N-(2,2,6,6-tetramethyl-piperidin-4-yl)-amino-methyl]-phenyl}sulphide, the 1:2 Ni²⁺ or Ca²⁺ complex ofdi-{2-hydroxy-5-t-octyl-3-[1,2,2,6,6-pentamethyl-piperidin-4-oxycarbonylmethyl]-phenyl}sulphide, the 1:1 Zn²⁺ complex ofdi-{2-hydroxy-5-[1,2,2,6,6-pentamethyl-piperidin-4-yl]-phenyl}sulphide.(4-amino-1,2,2,6,6-pentamethylpiperidine)₃, the 1:2 Ni²⁺complex of di-{2-hydroxy-5-[2,2,6,6-tetramethylpiperidin-4-yl]-phenyl}sulphide, the 1:1 Ca²⁺ or Ni²⁺ complex ofdi-{2-hydroxy-5-t-octyl-3-[2,2,6,6-tetramethyl-piperidin-4-oxy-carbonyl-methyl]-phenyl}sulphide.(4-amino-2,2,6,6-tetramethyl-piperidine)₃ and the 1:1 Ni²⁺complex ofdi-{2-hydroxy-5-t-octyl-3-[N-(2,3,6-trimethyl-2,6-diethyl-piperidin-4-yl)-amino]-phenyl}sulphide.(triethanolamine)₃.

Further preferred metal complexes are those of the formula XV

    [M.sup.q⊕ ] [L.sub.2.sup.r⊖ ].sub.q/r ·mA (XV)

in which M is Mg²⁺, VO²⁺, Ca²⁺, Mn²⁺, Zn²⁺, Co²⁺, Ni²⁺ or Al³⁺ and q is2 or 3 and L₂ is a t-dentate group of the formula IVb, which issubstituted by at least one group of the formulae Va, Vb or VI, and t is2, and R₁₅ and R₁₆ independently of one another are hydrogen, C₁ -C₁₈alkyl, which can be unsubstituted or substituted by a group of theformulae Va, Vb or Vc, or a group Vc, or a group of the formula VI inthe p-position, halogen or a radical of the formula --OR₂₄, or R₁₅ andR₁₆ together form a 1,3-butadiene-1,4-diyl radical, and R₅ is hydrogen,methyl or phenyl and Y is hydrogen, oxyl, C₁ -C₁₂ alkyl, C₃ -C₁₂alkenyl, C₃ -C₆ alkynyl, C₂ -C₂₁ alkoxyalkyl, C₇ -C₉ aralkyl,2,3-epoxypropyl, an aliphatic C₁ -C₄ acyl group or one of the groups--CH₂ COOR₆, --CH₂ --CH(R₇)--OR₈, --COOR₉ or --CONHR₉, in which R₆ is C₁-C₁₂ alkyl, C₃ -C₆ alkenyl, phenyl, C₇ -C₈ aralkyl or cyclohexyl and R₇is hydrogen, methyl or phenyl and R₈ is hydrogen, an aliphatic C₁ -C₁₈acyl group or an aromatic C₇ acyl group, an araliphatic C₈ -C₉ acylgroup or an alicyclic C₆ -C₉ acyl group, in which the aromatic part canbe unsubstituted or substituted by chlorine, C₁ -C₄ alkyl, C₁ -C₈ alkoxyand/or hydroxyl, and R₉ is C₁ -C₁₂ alkyl, cyclohexyl, phenyl or benzyl,and X₁ and X₂ independently of one another are --O-- or ##STR21## andR₂₁ is hydrogen or C₁ -C₈ alkyl and R₂₂ is hydrogen or a group --X₁ R₂₆,and Z is --O-- or ##STR22## and R₂₃ is C₁ -C₁₈ alkyl, C₃ -C₆ alkenyl, C₃-C₄ alkynyl, C₅ -C₇ cycloalkyl, C₆ -C₁₀ aryl, C₇ -C₁₄ aralkyl, C₇ -C₁₄alkylphenyl or a group of the formula VI, in which Y and R₂₁ are asdefined, and R₂₄ is hydrogen or C₁ -C₈ alkyl, C₅ -C₇ cycloalkyl, C₆ -C₁₄aryl, C₇ -C₁₄ aralkyl or C₂ -C₁₂ alkenyl which are unsubstituted orsubstituted by a group of the formula Vc, in which X₂ and R₂₃ are asdefined; or an aliphatic C₁ -C₁₈ acyl group, aromatic C₇ acyl group,araliphatic C₈ -C₉ acyl group or alicyclic C₆ -C₉ acyl group, which isunsubstituted or substituted by chlorine, C₁ -C₈ alkyl, C₁ -C₈ alkoxy, agroup Vc and/or hydroxyl, and R₂₅ is hydrogen, C₁ -C₁₈ alkyl, which canbe unsubstituted or substituted by a group of the formula Vc, in whichX₂ and R₂₃ are as defined, or C₃ -C₆ alkenyl, C₃ -C₄ alkynyl, C₅ -C₇cycloalkyl, C₆ -C₁₀ aryl, C₇ -C₁₄ aralkyl, a group of the formula CH₂--CH(R₅)--OR₂₆ or a group of the formula VI and R₂₆ is hydrogen, C₁ -C₁₈alkyl, C₃ -C₆ alkenyl, cyclohexyl, benzyl or an aliphatic C₁ -C₁₈ acylgroup, aromatic C₇ acyl group, araliphatic C₈ -C₉ acyl group oralicyclic C₆ -C₉ acyl group, which is unsubstituted or substituted bychlorine, C₁ -C₈ alkyl, C₁ -C₈ alkoxy and/or hydroxyl, and R₁₇ ishydrogen, C₁ -C₁₈ alkyl, halogen, a group --OR₂₄, or a group of theformula Vc in which R₂₃, R₂₄ and X₂ are as defined, and r is 1 and m isan integer from 0 to 2, the sum (2.q)+m being equal to the coordinationnumber of the metal ion M, and A is H₂ O or an amine of the formula III,in which R₁₂ is unsubstituted or --OH-substituted C₁ -C₁₈ alkyl, C₅ -C₁₂cycloalkyl, C₆ -C₁₈ aryl, C₇ -C₂₀ aralkyl, a substituted orunsubstituted aminoalkyl group or a piperidinyl group and R₁₃ ishydrogen or unsubstituted or --OH-substituted C₁ -C₁₈ alkyl, C₅ -C₁₂cycloalkyl, a substituted or unsubstituted aminoalkyl group or apiperidinyl group, or R₁₂ and R₁₃ together with the N atom form apyrrolidine, piperidine or morpholine ring which is substituted by alkylgroups or is unsubstituted, and R₁₄ is hydrogen or unsubstituted or--OH-substituted C₁ -C₁₈ alkyl.

Amongst the compounds of the formula XV, those to be mentioned inparticular are those in which M is Ca²⁺, Mn²⁺, Zn²⁺, Co²⁺, Ni²⁺ or Al³⁺and q is 2 or 3 and L₂ and t are as defined above, and R₁₅ and R₁₆independently of one another are hydrogen or C₁ -C₈ alkyl, which can beunsubstituted or substituted by a group of the formulae Va, Vb or Vc; ora group Vc or a radical --OR₂₄, and R₅ is hydrogen or methyl and Y ishydrogen, C₁ -C₄ alkyl, C₃ -C₆ alkenyl, propargyl, C₂ -C₅ alkoxyalkyl,benzyl, acetyl or one of the groups --CH₂ COOR₆, --CH₂ CH(R₇)--OR₈,--COOR₉ or --CONHR₉, in which R₆ is C₁ -C₄ alkyl and R₇ is hydrogen ormethyl and R₈ is hydrogen and R₉ is C₁ -C₄ alkyl, and X₁ and X₂independently of one another are --O-- or ##STR23## and R₂₁ is hydrogenor C₁ -C₄ alkyl and R₂₂ and Z are as defined above, and R₂₃ is C₁ -C₁₈alkyl, allyl, propargyl, cyclohexyl, phenyl, 4-t-butylphenyl or a groupof the formula VI, in which Y and R₂₁ are as defined, and R₂₄ ishydrogen or C₁ -C₁₂ alkyl, C₂ -C₆ alkenyl, cyclohexyl, phenyl or benzyl,which are unsubstituted or substituted by a group of the formula Vc, inwhich X₂ and R₂₃ are as defined, and R₂₅ is hydrogen, C₁ -C₁₂ alkyl,which can be unsubstituted or substituted by a group of the formula Vc,in which X₂ and R₂₃ are as defined, or allyl, propargyl, cyclohexyl,phenyl, benzyl or a group --CH₂ --CH(R₅)--OH, in which R₅ is as defined,and R₁₇ is hydrogen, C₁ -c₁₂ alkyl, a radical --OR₂₄ or a group of theformula Vc, in which R₂₃, R₂₄ and X₂ are as defined, and r and m andalso the sum (2.q)+m are as defined above, and A is H₂ O or an amine ofthe formula III, in which R₁₂ and R₁₃ independently of one another areC₁ -C₈ alkyl, C₁ -C₆ hydroxyalkyl or a substituted aminoalkyl group ofthe formul a IId ##STR24## in which v is 1 to 8 and Y, R₅ and R₂₁ are asdefined, or R₁₂ and R₁₃ together form a piperidine group, and R₁₄ ishydrogen or C₁ -C₈ alkyl or C₁ -C₆ hydroxyalkyl.

Particularly preferred compounds of the formula XV are those in which Mis Ca²⁺, Zn²⁺ or Ni²⁺ and q is 2 and L₂ is a t-dentate group of theformula IVb, which is substituted by at least one group of the formulaeVa or VI, and t is 2, and R₁₅ is hydrogen, C₁ -C₅ alkyl, a radical--OR₂₄, C₁ -C₄ alkyl substituted by a group Va or Vc, or a group Vc andR₁₆ is hydrogen or C₁ -C₈ alkyl and R₁₇ is hydrogen, and R₅ is hydrogenor methyl and Y is hydrogen, methyl or acetyl and X₁ is ##STR25## and X₂is --O-- and R₂₁ is hydrogen or methyl and R₂₃ is a group of the formulaVI, and R₂₄ is C₁ -C₄ alkyl substituted by a group of the formula Vc, inwhich X₂ and R₂₃ are as defined, and R₂₅ is hydrogen, C₁ -C₁₂ alkyl,cyclohexyl, benzyl or --CH₂ --CH(R₅)--OH, and r, m, the sum (2.q)+m, A,R₁₂, R₁₃ and R₁₄ are as defined.

Compounds of very particular interest are those of the formula XV inwhich R₁₅ is a C₁ -C₄ alkyl group which is in the o-position relative tothe hydroxyl group and is substituted by a group of the formula Va, orespecially also a group of the formula --OR₂₄ which is in the m-positionrelative to the hydroxyl group and in which R₂₄ is a C₁ -C₄ alkyl groupsubstituted by a group of the formula Vc, and R₁₆ and R₁₇ are hydrogen.

Examples of compounds of the formula XV are: the 1:2 Ni²⁺ complex of2-(2'-hydroxy-5'-t-butylphenyl)-5-(N-benzyl-2,2,6,6-tetramethyl-piperidin-4-oxycarbonyl)-benztriazole.((triethanomaine)₂, the 1:2 Ca²⁺ complex of2-{2'-hydroxy-5'-t-butyl-4'-[2*-di-(1,2,2,6,6-pentamethyl-piperidin-4-oxycarbonyl)-hexyl]-phenyl}-benztriazole.(4-amino-2,2,6,6-tetramethyl-piperidine)₂, the 1:2 Zn²⁺ complex of2-{2'-hydroxy-5'-sec-butyl)-4'-[2*-di-(1-acetyl-2,2,6,6-tetramethyl-piperidin-4-oxy-carbonyl)-hexyl]-phenyl}-4-(1-acetyl-2,2,6,6-tetramethyl-piperidin-4-oxycarbonyl)-benztriazole.(4-dimethylamino-2,2,6,6-tetramethyl-piperidine)₂ and the 1:2 Ni²⁺complex of2-{2'-hydroxy-3'-sec-butyl)-4'-[1,2,2,6,6-pentamethyl-piperidin-4-oxycarbonyl]-phenyl}-benzriazole.(N,N'-methyl-N,N'-(1,2,2,6,6-pentamethyl-piperidin-4-yl)-ethylenediamine.

Further preferred metal complexes are those of the formula XVI

    [M.sup.q⊕ ][L.sub.3.sup.r⊖ ].sub.q/r ·mA (XVI)

in which M is Mg²⁺, VO²⁺, Ca²⁺, Mn²⁺, Zn²⁺, Co²⁺, Ni²⁺ or Al³⁺ and q is2 or 3 and L₃ is a t-dentate group of the formula IVc, which issubstituted by at least one group of the formulae Va, Vb or VI, and t is2 or 4, and R₁₅ and R₁₆ indepdendently of one another are hydrogen or C₁-C₁₈ alkyl, which can be unsubstituted or substituted by a group of theformulae Va, Vb or Vc; or a group Vc, a group of the formula VI in thep-position, halogen or a radical --OR₂₄, or R₁₅ and R₁₆ together form a1,3-butadiene-1,4-diyl radical, and R₅ is hydrogen, methyl or phenyl andY is hydrogen, oxyl, C₁ -C₁₂ alkyl, C₃ -C₁₂ alkenyl, C₃ -C₆ alkynyl,C₂ - C₂₁ alkoxyalkyl, C₇ -C₉ aralkyl, 2,3-epoxypropyl, an aliphatic C₁-C₄ acyl group or one of the groups --CH₂ COOR₆, --CH₂ --CH(R₇)--OR₈,--COOR₉ or --CONHR₉, in which R₆ is C₁ -C₁₂ alkyl, C₃ -C₆ alkenyl,phenyl, C₇ -C₈ aralkyl or cyclohexyl and R₇ is hydrogen, methyl orphenyl and R₈ is hydrogen, an aliphatic C₁ -C₁₈ acyl group or anaromatic C₇ acyl group, an araliphatic C₈ -C₉ acyl group or an alicyclicC₆ -C₉ acyl group, in which the aromatic part can be unsubstituted orsubstituted by chlorine, C₁ -C₄ alkyl, C₁ -C₈ alkoxy and/or hydroxyl,and R₉ is C₁ -C₁₂ alkyl, cyclohexyl, phenyl or benzyl, and X₁ and X₂independently of one another are --O-- or ##STR26## and R₂₁ is hydrogenor C₁ -C₈ alkyl and R₂₂ is hydrogen or a group --X₁ R₂₆ and Z is --O--or ##STR27## and R₂₃ is C₁ -C₁₈ alkyl, C₃ -C₆ alkenyl, C₃ -C₄ alkynyl,C₅ -C₇ cycloalkyl, C₆ -C₁₀ aryl, C₇ -C₁₄ aralkyl, C₇ -C₁₄ alkylphenyl ora group of the formula VI, in which Y and R₂₁ are as defined, and R₂₄ ishydrogen or C₁ -C₈ alkyl, C₅ -C₇ cycloalkyl, C₆ -C₁₄ aryl, C₇ -C₁₄aralkyl or C₂ -C₁₂ alkenyl, which are unsubstituted or substituted by agroup of the formula Vc, in which X₂ and R₂₃ are as defined; or analiphatic C₁ -C₁₈ acyl group, aromatic C₇ acyl group, araliphatic C₈ -C₉acyl group or alicyclic C₆ -C₉ acyl group, which is unsubstituted orsubstituted by chlorine, C₁ -C₈ alkyl, C₁ -C₈ alkoxy, a group Vc and/orhydroxyl, and R₂₅ is hydrogen, C₁ -C₁₈ alkyl, which can be unsubstitutedor substituted by a group of the formula Vc, in which X₂ and R₂₃ are asdefined, or C₃ -C₆ alkenyl, C₃ -C₄ alkynyl, C₅ -C₇ cycloalkyl, C₆ -C₁₀aryl, C₆ -C₁₄ aralkyl, a group of the formula CH₂ --CH(R₅)--OR₂₆ or agroup of the formula VI, and R₂₆ is hydrogen, C₁ - C₁₈ alkyl, C₃ -C₆alkenyl, cyclohexyl, benzyl or an aliphatic C₁ -C₁₈ acyl group, aromaticC₇ acyl group, araliphatic C₈ -C₉ acyl group or alicyclic C₆ -C₉ acylgroup, which is unsubstituted or substituted by chlorine, C₁ -C₈ alkyl,C₁ -C₈ alkoxy and/or hydroxyl, and R₁₈ is a group --N(R₂₅)R₂₇ and R₁₉ ishydrogen, or R₁₈ and R₁₉ together are ═O or ═NR₂₇, and R₂₀ is hydrogen,C₇ -C₁₄ aralkyl, C₇ -C₁₄ alkylphenyl or C₁ -C₁₈ alkyl, C₂ -C₁₂ alkenyl,C₅ -C₁₂ cycloalkyl or C₆ -C₁₄ aryl, which are unsubstituted orsubstituted by a group of the formula Vc, or a group of the formula VIIor, if R₁₈ and R₁₉ together are ═O, a group of the formula Va; in whichX₁ , R₂₁ and Y are as defined above, and R₂₈ is C₁ -C₁₂ alkylene,butenylene, C₆ -C₁₀ arylene or diphenylene, and R₂₇ is hydrogen, C₇ -C₁₄aralkyl, C₇ -C₁₄ alkylphenyl, a group --OR₂₄, or C₁ -C₁₈ alkyl, C₂ -C₁₂alkenyl, C₅ -C₁₂ cylcoalkyl or C₆ -C₁₄ aryl which are unsubstituted orsubstituted by a group of the formula Vc, or a group of the formula VIor a group of the formula --CH₂ --CH(R₅)--OR₂₆ ; or, if R₂₀ is not agroup of the formula VII, R₂₇ is also a group of the formula VIIIa orVIIIb, and r is 1 or 2 and m is a number from 0 to 2, the sum (t.q/r)+mbeing equal to the coordination number of the metal ion M, and A is H₂ Oor an amine of the formula III, in which R₁₂ is unsubstituted or--OH-substituted C₁ -C₁₈ alkyl, C₅ -C₁₂ cycloalkyl, C₆ -C₁₈ aralkyl, C₇-C₂₀ aralkyl, a substituted or unsubstituted aminoalkyl group or apiperidinyl group and R₁₃ is hydrogen or unsubstituted or--OH-substituted C₁ -C₁₈ alkyl, C₅ -C₁₂ cycloalkyl, a substituted orunsubstituted aminoalkyl group or a piperidinyl group, or R₁₂ and R₁₃together with the N atom form a pyrrolidine, piperidine or morpholinering which is substituted by alkyl groups or is unsubstituted, and R₁₄is hydrogen or unsubstituted or --OH-substituted C₁ -C₁₈ alkyl.

Amongst the compounds of the formula XVI, those to be mentioned inparticular are those in which M is Ca²⁺, Mn²⁺, Zn²⁺, Co²⁺, Ni²⁺ or Al³⁺and q is 2 or 3 and t is 2 and L₃ is as defined above, and R₁₅ and R₁₆independently of one another are hydrogen or C₁ -C₈ alkyl, which can beunsubstituted or substituted by a group of the formulae Va, Vb or Vc; ora group Vc or a radical --OR₂₄, and R₅ is hydrogen or methyl and Y ishydrogen, C₁ -C₄ alkyl, C₃ -C₆ alkenyl, propargyl, C₂ -C₅ alkoxyalkyl,benzyl, acetyl or one of the groups --CH₂ COOR₆, --CH₂ CH(R₇)--OR₈,--COOR₉ or --CONHR₉, in which R₆ is C₁ -C₄ alkyl and R₇ is hydrogen ormethyl and R₈ is hydrogen and R₉ is C₁ -C₄ alkyl, and X₁ and X₂independently of one another are --O-- or ##STR28## and R₂₁ is hydrogenor C₁ -C₄ alkyl and R₂₂ and Z are as defined above, and R₂₃ is C₁ -C₁₈alkyl, allyl, propargyl, cyclohexyl, phenyl, 4-t-butylphenyl or a groupof the formula VI, in which Y and R₂₁ are as defined, and R₂₄ ishydrogen or C₁ -C₁₂ alkyl, C₂ -C₆ alkenyl, cyclohexyl, phenyl or benzyl,which are unsubstituted or substituted by a group of the formula Vc, inwhich X₂ and R₂₃ are as defined, and R₂₅ is hydrogen, C₁ -C₁₂ alkyl,which can be unsubstituted or substituted by a group of the formula Vc,in which X₂ and R₂₃ are as defined, or allyl, propargyl, cyclohexyl,phenyl, benzyl or a group --CH₂ --CH(R₅)--OH, in which R₅ is as defined,and R₁₈ is a group --N(R₂₅)R₂₇ and R₁₉ is hydrogen, or R₁₈ and R.sub. 19together are ═O or ═NR₂₇, and R₂₀ is hydrogen or C₁ -C₁₂ alkyl, C₂ -C₆alkenyl, cyclohexyl or phenyl, which are unsubstituted or substituted bya group of the formula Vc, and, if R₁₈ and R₁₉ together are ═O, R₂₀ is agroup of the formula Va, and R₂₇ is hydrogen or C₁ -C₁₂ alkyl, C₂ -C₆alkenyl, cyclohexyl or phenyl, which are unsubstituted or substituted bya group of the formula Vc; or R₂₇ is a group of the formula VI, and r is1 and m is a number from 0 to 2, the sum (2.q)+m being equal to thecoordination number of the metal ion M, and A is H₂ O or an amine of theformula III, in which R₁₂ and R₁₃ independently of one another are C₁-C₈ alkyl, C₁ -C₆ hydroxyalkyl or a substituted aminoalkyl group of theformula IId ##STR29## in which v is 1 to 8 and Y, R₅ and R₂₁ are asdefined, or R₁₂ and R₁₃ together form a piperidine group, and R₁₄ ishydrogen or C₁ -C₈ alkyl or C₁ -C₆ hydroxyalkyl.

Particularly preferred compounds of the formula XVI are those in which Mis Ca²⁺, Zn²⁺ or Ni²⁺ and q is 2 and L is a t-dentate group of theformula IVc, which is substituted by at least one group of the formulaVI, and t is 2, and R₁₅ and R₁₆ are hydrogen and R₁₈ is a group--N(R₂₅)R₂₇, in which R₂₅ is hydrogen, C₁ -C₁₂ alkyl or a group --CH₂--CH(R.sub. 5)--OH, in which R₅ is hydrogen or methyl, and R₂₇ ishydrogen or C₁ -C₄ alkyl substituted by a group of the formula Vc, or agroup of the formula VI, and X₂ is --O-- and Y is hydrogen, methyl oracetyl and R₂₁ is hydrogen or methyl and R₂₃ is a group of the formulaVI, and R₁₉ is hydrogen and R₂₀ is hydrogen or C₁ -C₄ alkyl, and r, m,A, R₁₂, R₁₃ and R₁₄ are as defined above.

Pariticularly preferred compounds of the formula XVI are also those inwhich M is Ca²⁺, Zn²⁺ or Ni²⁺ and q is 2 and L is a t-dentate group ofthe formula IVc, which is substituted by at least one group of theformulae Va or VI, and t is 2 and R₁₈ and R₁₉ together are ═O, and R₁₅is hydrogen, C₁ -C₄ alkyl, which is unsubstituted or substituted by agroup of the formulae Va or VI, or a group Vc or a radical --OR₂₄ andR₁₆ is hydrogen and X₁ is ##STR30## and R₂₁ is hydrogen or methyl and Yis hydrogen, methyl or acetyl, and R₂₄ is C₁ -C₄ alkyl substituted by agroup of the formula Vc, and R₂₃ is a group of the formula VI and X₂ is--O--, and R₂₀ is hydrogen, C₁ -C₅ alkyl, or C₁ -C₄ alkyl or C₂ alkenylsubstituted by a group of the formula Vc, or a group of the formulae Va,in which X₂, R₂₁ and Y are as defined, and R₂₅ is hydrogen, C₁ -C₁₂alkyl or a group --CH₂ --CH(R₅)--OH, in which R₅ is hydrogen or methyl,and r, m, A, R₁₂, R₁₃ and R₁₄ are as defined above.

Particularly preferred compounds of the formula XVI are also those inwhich M is Ca²⁺, Zn²⁺ or Ni²⁺ and q is 2 and L is a t-dentate group ofthe formula IVc, which is substituted by at least one group of theformula Va or VI, and t is 2, and R₁₈ and R₁₉ together are ═NR₂₇, andR₁₅ is hydrogen, C₁ -C₄ alkyl, which is unsubstituted or substituted bya group of the formulae Va or VI, or a group Vc or a radical --OR₂₄ andR₁₆ is hydrogen, and X₁ is ##STR31## and R₂₁ is hydrogen or methyl and Yis hydrogen, methyl or acetyl, and R₂₄ is C₁ -C₄ alkyl substituted by agroup of the formula Vc, and R₂₃ is a group of the formula VI, and X₂ is--O-- and R₂₀ is hydrogen, C₁ -C₅ alkyl or C₁ -C₄ alkyl which issubstituted by a group of the formula Vc, and R₂₅ is hydrogen, C₁ -C₁₂alkyl or a group --CH₂ --CH(R₅)--OH, in which R₅ is hydrogen or methyl,and R₂₇ is a group of the formula VI, and r, m, A, R₁₂, R₁₃ and R₁₄ areas defined above.

Examples of compounds of the formula XVI are: the 1:2 Ni²⁺ complex ofN-methyl-N-(2-hydroxyphenyl)-N-[1',2',2',6',6'-pentamethyl-piperidin-4'-oxy-carbonylmethyl]azomethine.(4-amino-2,2,6,6-tetramethyl-piperidine)₂, the 1:3 Al³⁺ complex ofN-phenyl-N-(2-hydroxyphenyl)-N-[2'-(1-benzyl-2,2,6,6-tetramethyl-piperidin-4-oxy-carbonyl)-phenyl]-azomethine,the 1:1 Ni²⁺ complex ofhexamethylene-di-{N-methyl-[2-hydroxy-5-(1',2',2',6',6'-pentamethyl-piperidin-4'-yl)]}-azomethine.(triethanolamine)₂, the 1:2 Ca²⁺ complex ofN-(1,2,2,6,6-pentamethyl-piperidin-4-yl)-N-n-butyl-N-([2'-hydroxy-5'-t-octyl]-benzyl)-amine.(dibenzylpropylamine)₂, the 1:2 Ni²⁺ complex ofhexamethylene-di-{N-[2-hydroxy-4-(1'-hexyl-2',2',6',6'-tetramethyl-piperidin-4'-oxy-carbonylmethyl-oxy)]}-benzylamine.(triethanolamine)₂, the 1:2 Mg²⁺ complex of2-{1',2',2',6',6'-pentamethyl-piperidin-4-oxycarbonyl}-4-{1',2',2',6',6'-pentamethyl-piperidin-4-oxycarbonyl-methyl-oxy}-phenol.(4-dimethylamine-2,2,6,6-tetramethyl-piperidine)₂ and the 1:2 Ni²⁺complex of2-methyl-carbonyl{-3,5-di-2',2',6',6'-tetramethyl-piperidin-4-oxycarbonyl-methyloxy}-phenol.(triethanolamine)₂.

The preparation of the compounds of the formula I is known.

Thus, the compounds of the formula I in which s and m are 0 are obtainedmost simply by reacting approximately one mol of the free ligand[L]H_(r) with approximately r/_(q) * mols of an alkali metal hydroxide,alcoholate, hydride or amide or of an alkaline earth metal hydroxide,alcoholate, hydride or amide or with r/_(2q) * mols of an alkali metalcarbonate or alkaline earth metal carbonate, in an inert organicsolvent. The reaction can be carried out at room temperature or, inorder to accelerate the conversion, at elevated temperatures up to thereflux temperature. The reaction is most simply carried out at roomtemperature. Alkali metals which can be used are, especially, lithium,sodium, potassium or rubidium, in particular sodium or potassium. Asuitable alkaline earth metal is, especially, calcium. q* defines thecharge on the alkali metal cation or alkaline earth metal cation M*used. Suitable inert organic solvents are alcohols, such as methanol orethanol, ethers, such as dioxane, tetrahydrofurane or diethyl ether,aromatic hydrocarbons, such as benzene, toluene or xylene, aliphatichydrocarbons, such as hexane or ligroin, or amides, such asdimethylformamide or hexamethylphosphoric acid triamide.

The alkali metal salts or alkaline earth metal salts [L]M*_(r/q*)obtained in this way can then be reacted in a simple manner with a metalsalt ML*_(q). For this reaction, in particular, q/r mols of the compound[L]M*_(r/q*) are employed per mol of ML*_(q), in an inert organicsolvent. Suitable solvents are those described above. The temperaturecan again be chosen between room temperature and the reflux temperature.Anions suitable as the anion L* are, especially, halides, in particularchloride, or carboxylate anions, such as acetate or caproate.

It is also possible to combine the two process steps described above orto employ hydrates of the compounds described.

If, for example, a hydroxide or carbonate is used as ML*_(q), it is evenpossible to dispense with the formation of the alkali metal salts oralkaline earth metal salt.

If s is not 0, the procedure is, in principle, as described and (q-s)/rmols of a compound [L]M*_(r/q) and s mols of a compound BM* are reactedwith a metal salt of the formula ML*_(q). The same result is achieved bymeans of ligand replacement reactions, for which, for example, MB_(q)and (q-s)/r mols of [L]M*_(r/q) are employed. The compounds B are knownand can be prepared by known methods.

If the compound of the formula I is to contain an amine A, the simplestprocedure is to heat a solution of the compound [M^(q+) ][L^(r-)].sub.(q-s)/r. [B⁻ ]_(s), the preparation of which has been describedabove, in one of the aprotic inert solvents described, in the presenceof at least m mols of the compound A. The temperature can be up to thereflux temperature but in any case should be at least 30° C.Advantageous results are achieved by boiling under reflux, in which casea water separator is used.

The amines A are known and can be prepared by known methods. Somecompounds of this type are described, for example, in U.S. Pat. No.3,901,031 or, if A contains piperidyl radicals, also in GermanOffenlegungsschrift No. 2,349,962.

The condition which a chelate-forming ligand according to the presentinvention has to meet is that it contains at least one group of theformula IIa or IIb. The methods by which compounds which contain groupsIIa or IIb are obtained has been described in the literature. Thus, forexample, derivatives of pyrrolidine are described in GermanOffenlegungsschrift No. 2,459,331; derivatives of imidazolidine aredescribed in German Offenlegungsschrift No. 2,427,853 or GermanOffenlegungsschrift No. 2,500,313; derivatives of1,4-diazacycloheptanone are described in German Offenlegungsschrift No.2,428,877 or German Offenlegungsschrift No. 2,621,924: derivatives ofpiperazine are described in German Offenlegungsschrift No. 2,315,042;derivatives of 1-aza-4-thiacyclohexane are described in GermanOffenlegungsschrift No. 1,351,865; derivatives of dipiperidyl aredescribed in German Offenlegungsschrift No. 2,425,984 and derivatives ofpiperidine are described, for example, in German OffenlegungsschriftenNos. 2,258,752, 2,040,975 and 2,227,689, U.S. Pat. Nos. 3,639,409 and3,640,928 or British Pat. No. 1,262,234.

As already mentioned, those chelate-forming agents which contain one ormore piperidine radicals are of particular interest. This is alsoindicated by the fact that the particularly preferred compounds containgroups of the formula Va, Vb or VI, which are obtained, for example, asfollows:

If the group concerned is a group of the formula Va or VI, thecorresponding 4-hydroxypiperidines (known from GermanOffenlegungsschrift No. 2,352,658) or the 4-aminopiperidines (known fromU.S. Pat. No. 3,684,765) can be used as the starting materials. The 4-OHcompounds can generally be prepared from the 4-oxopiperidines of theformula XVII ##STR32## in which R₂₁ and Y are as defined above, byreduction, for example catalytic hydrogenation over Raney nickel, whilstthe 4-NH₂ compounds are obtainable, for example, from a compound of theformula XVII by means of reductive reaction with ammonia.

The 4-oxopiperidines of the formula XVII, in which Y is hydrogen, can beprepared by various processes.

Thus, for example, the reaction of an aliphatic ketone with ammonia isdescribed by W. Traube in Chem. Ber. 41, 777 (1908).

4-Oxopiperidines of the formula XVII in which Y is hydrogen can also beprepared analogously to the process described in U.S. Pat. No.3,513,170. In this case, an alkyl-substituted tetrahydropyrimidine isrearranged hydrolytically in the presence of an acid catalyst.

N-H compounds of the formula XVII, which have different substituents inthe 2-position and in the 6-position, can be prepared by reacting aketone of the formula CH₃ --CO--CH₂ R₂₁ with ammonia. The pyrimidineformed is hydrolysed to an aminoketone of the formula XVIII, asdescribed in Helv. Chim. Acta 30, 114 (1947). ##STR33##

In a second process step, the compounds of the formula XVIII are reactedwith ammonia and a ketone CH₃ --CO--CH₂ --R₂₁, as has been described,for example, in Monatsh. Chemie 88, 464 (1957). The compounds of theformula XVII in which Y is hydrogen can be obtained by hydrolysis fromthe pyrimidine obtained in this way.

Compounds of the formula XVII in which Y is not hydrogen, or also thosewhich correspond to the protonated form of the group of the formula Vb,can be prepared from the corresponding N--H compounds by substitution.The reactions involved are the substitution reactions customary forsecondary amines, although, because of the steric hindrance resultingfrom the methyl group or the group --CH₂ --R₂₁, these reactions proceedmore slowly. N--H compounds can, for example, be reacted with alkylhalides, alkenyl halides, aralkyl halides or alkoxyalkyl halides, withdialkyl sulphates, with epichlorohydrins, with esters ofchloro-carboxylic acids, such as chloroacetates, or with acid chloridesor acid anhydrides.

The group --CH₂ --CH(R₇)--OR₈ can be introduced by reacting theN--H-piperidines with an epoxide of the formula ##STR34## andsubsequently acylating the reaction product with an acyl chloride of theformula R₈ Cl. A hydroxyalkyl radical can be introduced analogously.

Compounds of the2,2,6,6-tetramethyl-4-(alkoxycarbonylcyanomethyl)-piperidine type, whichcan be used as intermediates, are also known from British Pat.Specification No. 1,214,426.

A radical R₂₂ is introduced, starting from the 4-hydroxy- or4-amino-piperidines, by conventional methods, for example by reactionwith a chloride of the formula R₂₆ Cl or by a hydrogenolyticcondensation reaction with H₂ N--R₂₆.

The requirement to which the groups of the formula IIa, IIb, Va, Vb andVI, which have been described at the indicated points, are subject isthat they contain a functional group, especially an amino, hydroxyl orcarboxylic acid (ester) group, which makes it possible to incorporatethe groups mentioned into the chelate-forming molecule by means ofconventional trans-esterification or condensation reactions.

If these groups are, for example, in the substituents R₁₅ or R₁₆ asalkyl substituted by a group Va or Vb, in which Z is --O--, ahydroxyphenylalkyl chloride is reacted in a known manner with an alcoholor amine derived from the groups Va or Vb, in the presence of a base.The reaction with an alcoholate is also suitable and is known as theWilliamson synthesis. If, in the formula Vb, Z is --O--C(O)--, or if R₁₅or R₁₆ is a group of the formula Vc, in which R₂₃ is, for example, aradical VI, the introduction thereof is effected most simply by reactingaromatic carboxylic acids, for example benzoic acid, phenylacetic acidor β-phenylpropionic acid, with an alcohol derived from the formula Vaor Vb, by means of a conventional trans-esterification reaction. Thisreaction can be acid-catalysed or base-catalysed. If R₁₅ or R₁₆ is analkoxy group substituted by a radical of the formula Vc, theintroduction thereof is effected, for example, by reacting a phenol, forexample a procatechol, resorcinol, hydroquinone, pyrogallol orphloroglucinol, with a halogenoalkyl derivative of the group of theformula Vc in an inert solvent in the presence of a base. If R₁₅ or R₁₆is a group of the formula VI, a phenol is reacted with a 4-oxoderivative of a group of the formula VI in the presence of an acid andthe reaction product is subsequently reduced, as has also beendescribed, for example, in U.S. Pat. No. 3,847,930.

If L is a group of the formula IVa, the preparation thereof can beeffected analogously to the description in U.S. Pat. No. 2,971,941,approximately 2 mols of a phenol being reacted with 1 mol of SCl₂ andthe radicals R₁₅ and R₁₆ being introduced as described above, before orafter the SCl₂ stage. If R₁₅ is a group of the formula VI, this isintroduced before the SCl₂ stage. The chelate-forming agents H₂ Lcorresponding to the formula IVa which are prepared in this way arenovel and therefore are also a subject of the present invention. Acharacteristic of compounds which contain a group of the formula IVa isthat r can have a value of 1 or 2. This is dependent on the ratio of theconcentration in which the free ligand is employed and on the metal saltin the chelating step described above.

If L is a group of the formula IVb, this can be prepared analogously tothe compounds of British Pat. No. 878,362 or British Pat. No. 1,332,560.If R₁₅ or R₁₆ contains a group IIa or IIb, or, respectively, a group Va,Vb or VI, these are introduced as described above. If R₁₇ is a group ofthe formula Vc, in which R₂₃ is a radical of the formula VI, the knowncompounds in which R₂₃ is alkyl are used as the starting materials andthese are trans-esterified in a known manner with an alcohol derivedfrom the group Va. If R₁₇ is a group of the formula --OR₂₄, the simplestprocedure is to react the analogous compound in which R.sub. 17 ishydroxyl with a compound ClR₂₄. Some of the chelate-forming agents ofthe formula IVb are known from Japanese Published Specification No.51-88,484.

If L is a group of the formula IVc, R₁₅ or R₁₆ are introduced asdescribed, if these contain a group IIa or IIb or, respectively Va, Vbor VI.

If R₁₈ and R₁₉ together are ═0, the starting materials used are as arule salicyclic acid or its alkyl esters, salicylamide or anα-hydroxyphenyl ketone. The introduction of a group of the formula Va asR₂₀ is therefore effected, using a salicyclate as the starting material,by a simple transesterification reaction with an alcohol or amine whichis derived from the formula Va. Compounds in which R₂₀ is an alkyl,alkenyl, cycloalkyl or aryl group substituted by a group of the formulaVc can be prepared in an analogous manner by trans-esterification. Inorder to obtain the compounds in which R₂₀ is a group of the formulaVII, approximately 2 mols of a salicylate are reacted with approximately1 mol of a diol. The desired radicals R₁₅ and R₁₆ can be incorporated,in the maner indicated above, before or after this stage. Thechelate-forming agents of the formula IVc, in which R₁₈ and R₁₉ togetherare ═0, which are thus obtained, are novel compounds and therefore are asubject of the present invention.

The chelate-forming agents of the formula IVc, in which R₁₈ and R₁₉together are ═NR₂₇, can be prepared in a known manner from the ketocompounds thus obtained. For this purpose, the keto compounds arereacted with a primary amine in a conventional condensation reaction.The amine can be an amine which is derived from a group of the formulaVa, in which X₁ is ##STR35## or can also be an alkyl-, alkenyl-,cycloalkyl- or aryl-amine substituted by a group of the formula Vc. Theresulting compounds of the formula IVc, in which R₁₈ and R₁₉ togetherwith ═NR₂₇, are novel substances and therefore are also a subject of thepresent invention. The compounds in which R₂₇ is a group of the formulaVIIIb are obtained by replacing the primary amine by a diamine andallowing this to react with 2 mols of the keto compound.

The azomethine compounds of the formula IVc which have been describedcan be reduced to the compounds of the formula IVc in which X₁ is##STR36## by known reduction processes, for example by means of hydrogenon Pd/C. Another variant is to introduce a secondary amine HN(R₂₅)R₂₇ ina Mannich reaction in the presence of an aldehyde, preferablyformaldehyde. If the chelate-forming agent contains a group of theformula VIIIa as R₂₇, it is prepared by reduction of the correspondingdi-azomethine compound. The compounds of the formula IVc in which R₁₈ is--N(R₂₅)R₂₇, which are obtained in the manner described, are novel andtherefore are also a subject of the invention.

If the ligands used are those in which r=2, oligomers or even polymerscan form. A characteristic of these is that they contain several centerscapable of forming a chelate and therefore are able to bind severalmetal centres. Higher-molecular substances of this type aredistinguished by an increased stability to extraction. Higher-molecularsubstances of this type are novel and therefore are also a subject ofthe invention, as is indicated, in particular, by the fact that theratio, given in the formula I, of the metal to the ligand L is alsocorrect in this case if it is calculated for the structural unit onwhich the polymer is based. The molecular weight is approximately400-10,000 and preferably 400-2,000.

According to the present invention, the compounds of the formula I canbe used as stabilisers for plastics in order to protect them againstdamage by the action of oxygen, heat and light. Examples of suchplastics are the polymers listed on pages 12-14 of GermanOffenlegungsschrift No. 2,456,864.

The stabilising of polyolefines and styrene polymers and ofpolyurethanes is of particular importance, and the compounds of theformula I are outstandingly suitable for this. Examples of such polymersare high density and low density polyethylene, polypropylene,ethylene/propylene copolymers, polystyrene,styrene/butadiene/acrylonitril terpolymers, mixtures of polyolefines orof styrene polymers, and polyurethanes based on polyethers orpolyesters, in the form of films, fibres, lacquers, elastomers or foams.

The stabilisers are added to the plastics in a concentration of 0.01 to5% by weight, calculated relative to the material to be stabilised.Preferably, 0.03 to 1.5, and particularly preferentially 0.2 to 0.6% byweight of the compounds, calculated relative to the material to bestabilised, are incorporated into the latter.

Incorporation can be effected after polymerisation, for example bymixing the compounds and, if desired, further additives into the melt bythe methods customary in the art, before or during shaping, or byapplying the dissolved or dispersed compounds to the polymer, withsubsequent evaporation of the solvent if necessary.

The novel compounds can also be added to the plastics to be stabilisedin the form of a master batch which contains these compounds, forexample in a concentration of 2.5 to 25% by weight.

In the case of crosslinked polyethylene, the compounds are added priorto crosslinking.

The invention therefore also relates to the plastics stabilised by theaddition of 0.01 to 5% by weight of a compound of the formula I, whichplastics can, if desired, contain yet further known and customaryadditives. The plastics stabilised in this way can be employed in verydiverse forms, for example as films, fibres, tapes or profiles or asbinders for lacquers, adhesives or putties.

Examples which may be mentioned of further additives, together withwhich the stabilisers which can be used according to the invention canbe employed, are: antioxidants, such as simple 2,6-dialkylphenols,derivatives of alkylated hydroquinones, hydroxylated thiodiphenylethers, alkyldiene-bisphenols, O-, N- and S-benzyl compounds,hydroxybenzylated malonates, hydroxybenzyl-aromatic compounds,s-triazine compounds, amides ofβ-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propionic acid, esters ofβ-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propionic acid, esters ofβ-(5-tert.-butyl-4-hydroxy-3-methylphenyl)-propionic acid, esters of3,5-di-tert.-butyl-4-hydroxyphenylacetic acid, acylaminophenols,benzylphosphonates, aminoaryl derivatives, UV absorbers and lightstabilisers, such as 2-(2'-hydroxyphenyl)-benztriazoles,2,4-bis-(2'-hydroxyphenyl)-6-alkyl-s-triazines, 2-hydroxybenzophenones,1,3-bis-(2'-hydroxybenzoyl)-benzenes, esters of substituted orunsubstituted benzoic acids, and acrylates; and, furthermore, nickelcompounds, stearically hindered amines, oxalic acid diamides, metaldeactivators, phosphites, compounds which destroy peroxide, polyamidestabilisers, basic Co stabilisers, PVC stabilisers, nucleating agents orother additives, for example plasticisers, lubricants, emulsifiers,fillers, carbon black, asbestos, kaolin, talc, glass fibres, pigments,optical brighteners, flameproofing agents and antistatic agents.

Examples of further additives together with which the stabilisers whichcan be used according to the invention can be employed are given onpages 18-24 of German Offenlegungsschrift No. 2,427,853.

The preparation and use of the compounds according to the invention aredescribed in more detail in the examples which follow.

EXAMPLE 1

137.2 g (0.5 mol) ofN-[2-hydroxybenzyl]-N-methyl-N-[2,2,6,6-tetramethyl-piperidyl-4]-aminewere dissolved in 200 ml of ethanol and a solution of 11.5 g of Na in300 ml of ethanol was added dropwise at room temperature in the courseof 1.5 hours and the mixture was stirred for a further 1.5 hours at 50°C. 59.4 g of NiCl₂.2H₂ O, dissolved in 300 ml of ethanol, were addeddropwise in the course of 2 hours and the solution was then kept underreflux for 2 hours. The solvent was evaporated, the residue was taken upin hot hexane and the NaCl was filtered off. After cooling the hexanesolution, the stabiliser 1 crystallised out as a green-yellow colouredcompound. ##STR37## Ni calculated (relative to H₂ O): 9.26%. Ni found:9.67%.

found (relative to H₂ O): 4.5%.

The following compounds were prepared analogously to compound I.

    __________________________________________________________________________                               Ni calculated                                                                 (relative to                                                                          Ni found                                                                            H.sub.2 O                            Example                                                                            Stabiliser            H.sub.2 O %                                                                           %     %                                    __________________________________________________________________________          ##STR38##            10.00   9.2   1.3                                  3                                                                                   ##STR39##            10.26   9.9   3.9                                  4                                                                                   ##STR40##            9.14    8.57  0.6                                  5                                                                                   ##STR41##            8.8     7.96  4.2                                  6                                                                                   ##STR42##            9.7     9.67  4.4                                  __________________________________________________________________________

EXAMPLE 7

15.66 g ofdi-{2-hydroxy-5-t-octyl-3-[N-methyl-N-(2,2,6,6-tetramethylpiperidinyl-4)-aminomethyl]-phenyl}sulphide were dissolved in 100 ml of ethanol and 1.36 g of sodiumethylate were added under a nitrogen atmosphere. The reaction mixturewas stirred at room temperature for 20 minutes and 1.65 g of NiCl₂.2H₂O, dissolved in 40 ml of ethanol, were then added dropwise. The mixturewas stirred at 24° C. for 12 hours. The NaCl which had precipitated wasfiltered off and the solvent was evaporated. The 16.9 g of the palegreen stabiliser 7. ##STR43## thus obtained, gave the followinganalysis:

C₁₀₀ H₁₇₀ N₈ O₄ S₂.Ni.2H₀

Ni calculated (relative to H₂ O): 3.51%.

Ni found: 3.43%.

EXAMPLE 8

12.6 g [0.02 mol] of the Ni salt ofN-methyl-N-[2,2,6,6-tetramethyl-piperidinyl-4-]-amine and 4 g (0.02 mol)of N,N-dimethyl-N-[1,2,2,6,6-pentamethylpiperidyl-4]-amine weredissolved in 200 ml of toluene and the solution was kept under refluxfor 7 hours using a water separator. The solvent was then evaporatedoff, the residue was taken up in hot hexane and, after the solution hadcooled, the crystals formed were filtered off and dried in a vacuum ovenat 60° C. for 20 hours. The product ##STR44## gave the followinganalysis: Ni calculated (relative to H₂ O): 7.03%.

Ni found: 7.65%.

The compounds of the following types were prepared analogously tostabiliser 8: ##STR45##

The corresponding ligands A, used as amines, are listed in the examplesin the table which follows.

    ______________________________________                                                                 Ni                                                                            cal-                                                                          culated                                                                       (relative                                                                              Ni                                          Ex-                      to       found H.sub.2 O                             ample Amine A            H.sub.2 O) %                                                                           %     %                                     ______________________________________                                         9                                                                                   ##STR46##         6.9      6.69  3.7                                   10                                                                                   ##STR47##         5.69     6.13  3.0                                   11                                                                                   ##STR48##         6.03     6.45  2.9                                   ______________________________________                                    

The following compounds were prepared analogously to the stabiliseraccording to Example 8

    ______________________________________                                         ##STR49##                                                                                             (a) Ni                                                                        cal-                                                                          culated                                                                       (b) N                                                                         cal-     (a) Ni                                                               culated  found                                                                (relative                                                                              (b) N                                                                to       found H.sub.2 O                             Ex.  Amine A             H.sub.2 O) %                                                                           %     %                                     ______________________________________                                        12                                                                                  ##STR50##          (a) 7.86 (a) 7.09                                                                            2.6                                   13                                                                                  ##STR51##          (a) 6.73 (b) 11.54                                                                     (a) 5.78 (b) 11.4                                                                   2.1                                   14                                                                                  ##STR52##          (a) 6.36 (a) 5.76                                                                            2.1                                   15                                                                                  ##STR53##          (a) 7.51 (b) 9.66                                                                      (a) 5.85 (b) 9.13                                                                   2.03                                  ______________________________________                                    

The following compounds were prepared analogously to the stabiliseraccording to Example 8:

    ______________________________________                                         ##STR54##                                                                                               Ni                                                                            cal-                                                                          cu-                                                                           lated                                                                         (rel-                                                                         ative                                                                         to     Ni                                                                     H.sub.2 O)                                                                           found H.sub.2 O                             Ex.  Amin A                %      %     %                                     ______________________________________                                        16                                                                                  ##STR55##            6.89   6.51  0.5                                   17                                                                                  ##STR56##            4.61   5.11  <0.3                                  18                                                                                  ##STR57##            5.98   5.29  0.6                                   ______________________________________                                    

EXAMPLE 19

(a) 22.1 g of 3,3'-di-(t-octyl)-6,6'-diphenylsulphide and 26.8 g of4-n-octylamino-2,2,6,6-tetramethyl-piperidine were dissolved in 100 mlof ethanol; and 8.6 g of a 35% solution of formaldehyde were then addeddropwise at 23° C. under nitrogen. The reaction mixture was maintainedfor 4 hours at reflux temperature, and the solvent was subsequentlyevaporated off under vacuum to yield 35.2 g ofdi-{2-hydroxy-5-t-octyl-3-[N-octyl-N-(2,2,6,6-tetramethylpiperidyl-4)-aminomethyl]phenyl}-sulphide.

(b) 20.08 g of the product from Example 19a were treated analogously toExample 5 with sodium ethanolate (from 0.92 g of Na in 20 ml of ethanol)and 3.3 g of NiCl₂.2H₂ O. The resulting product: 21.3 g of Stabiliser 19##STR58## gave the following analysis values: C₆₄ H₁₁₂ N₄ O₂ S.Ni.2H₂ O:

Ni (calculated): 5.35%.

Ni (found): 5.1%.

EXAMPLE 20

13.3 g of Stabiliser 19 were taken up in 150 ml of ethanol, and 1.87 gof 4-amino-2,2,6,6-tetramethyl-piperidine in 20 ml of ethanol were addeddropwise at 24° C. in a nitrogen atmosphere; the reaction solution wassubsequently stirred for 16 hours. The solvent was then evaporated offto leave 15.0 g of green crystals (Stabiliser 20), ##STR59## which gavethe following analysis values: Ni (calculated): 4.83%.

Ni (found): 4.54%.

EXAMPLE 21

Freshly prepared sodium methylate (from 1.15 g of Na and 40 ml ofmethanol) was added to 19.7 g of(N-[2-hydroxy-4-t-octylbenzyl]-N-methyl-N-[2,2,6,6-tetramethyl-piperidinyl-4]-aminein 150 ml of methanol. After the mixture had been stirred for 1/2 hour,4.3 g of NiCl₂.2H₂ O in 50 ml of methanol were added dropwise, andstirring was continued for 5 hours at 24° C. The sodium was filtered offand the solvent evaporated off. The resulting greenish-brown residue##STR60## (Stabiliser 21) gave the following analysis values: Ni(calculated): 7.04%.

Ni (found): 7.28%.

EXAMPLE 22

52.5 g (0.1 mol) ofN-[2-hydroxybenzyl]-N-[2,2,6,6-tetramethyl-piperidyl-4]-amine weredissolved in 250 ml of methanol, and 100 ml of a 1 molar sodiummethylate solution were added. To this solution were then added dropwiseat room temperature, in the course of 1/2 hour, 25 ml of a 2 molarsolution of anhydrous nickel chloride in methanol (corresponding to 0.05mol of NiCl₂), and the reaction mixture was refluxed for 30 minutes. Thesodium chloride which had precipitated was filtered off, and thefiltrate was evaporated to dryness. The residue was extracted with etherat room temperature, the extract was concentrated by evaporation, anddried at 80° C. under a pressure of 11 mm Hg to yield a dark beigepowder of the following composition:

    ______________________________________                                         ##STR61##                                                                    (Stabiliser 22)                                                               ______________________________________                                        Ni    (calculated)                                                                             10.10 %   Ni  (found)                                                                              10.03 %                                 C     "          66.10 %   C   "      65.94 %                                 H     "           8.67 %   H   "      8.85 %                                  N     "           9.63 %   N   "      9.71 % .                                ______________________________________                                    

EXAMPLE 23

52.5 g (0.1 mol) ofN-[2-hydroxybenzyl]-N-[2,2,6,6-tetramethyl-piperidyl-4]-amine weredissolved in 250 ml of absolute ethanol, and to the solution were added100 ml of a 1 molar sodium methylate solution. A solution of 6.81 g(0.05 mol) of anhydrous zinc chloride in 20 ml of absolute methanol wasadded dropwise to the above solution; the mixture was refluxed for 11/2hours, and the solvent was subsequently evaporated off. The residue wasthen extracted with hot toluene; the extract was concentrated byevaporation and dried at 60° C. under a pressure of 11 mm Hg. There wasobtained a yellowish powder of the following composition:

    ______________________________________                                         ##STR62##                                                                

    ______________________________________                                        Zn    (calculated)                                                                             11.11 %   Zn  (found)                                                                             10.5/10.4 %                              C     "          65.35 %   C   "     64.42/64.39 %                            H     "           8.57 %   H   "      8.76/8.56 %                             N     "           9.53 %   N   "      9.07/9.14 % .                           ______________________________________                                    

EXAMPLE 24 Light-stabilising effect in high-pressure polyethylene sheets

100 parts of polyethylene granules of low density (=0.917) werehomogenised with 0.05 part of a stabiliser given in the following Tablein a Brabender plastograph for 10 minutes at 180° C. The mixture thusobtained was removed as quickly as possible from the kneader, andpressed in a toggle press to give a 2-3 mm thick sheet. A portion of theresulting pressed blank was cut out and pressed between two high-glosshard aluminium sheets, using a manually operated hydraulic laboratorypress, for 6 minutes at 170° C. under a pressure of 12 tons to obtain a0.1 mm thick sheet, which was immediately chilled in cold water.Specimens each 60×44 mm were then punched from this sheet and exposed inthe Xenotest 1200. These test specimens were removed from the exposureapparatus at regular intervals and their carbonyl content was tested inan IR spectrophotometer. The increase in the carbonyl extinction onexposure is a measure of the photooxidative degradation of the polymer(see L. Balaban et al., J. Polymer Sci., Part C, 22, 1059-1071 (1969);J. F. Heacock, J. Polymer Sci., Part A-1, 22, 2921-34 (1969) and D. J.Carlsson and D. M. Wiles, Macromolecules 2, 587-606 (1969), and fromexperience this increase is associated with a deterioration of themechanical properties of the polymer. The time taken to reach a carbonylextinction of 0.100 is taken as a measure of the protective action ofthe stabiliser used.

The results are summarised in Table I.

                  TABLE I                                                         ______________________________________                                                    Exposure time in hours until the                                  Stabiliser  carbonyl extinction is 0.1                                        ______________________________________                                        none         270 h                                                            No. 3       1630 h                                                            No. 10      1630 h                                                            No. 12      2100 h                                                            No. 11      1800 h                                                            ______________________________________                                    

EXAMPLE 25

100 parts of polypropylene powder (melt index 1.5 g/10 min., 230° C.,2160 g load) were mixed in a drum mixer with 0.1 part ofpentaerythritol-tetrakis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate]and 0.15 part of one of the stabilisers listed in the following TableII, and the mixture was extruded in an extruder at 200°-220° C. andgranulated. The granules were then processed in the customary manner bymeans of an extruder with a slot die into the form of sheets; these weresubsequently cut into ribbons and then stretched at elevated temperatureto six times their original length. The denier of these ribbons was700-900 den., their width 4 mm and their tensile strength 5.5-6.5 g/den.These ribbons were exposed in a Xenotest 1200. Specimens were subjectedat regular intervals to a tensile elongation test, by which was shownthat a progressive decrease in the tensile strength was occurring withincreasing exposure time. The exposure time until the tensile strengthhas decreased to half its initial value is lengthened by the action ofthe light stabilisers.

                  TABLE II                                                        ______________________________________                                                     Exposure time in the Xenotest                                                 1200 until the tensile strength                                               has decreased to half the                                        Stabiliser No.                                                                             initial value                                                    ______________________________________                                        none          400 h                                                           14           2300 h                                                           16           2030 h                                                           20           3950 h                                                           12           2100 h                                                           11           >2000 h                                                          10           3080 h                                                           15           2100 h                                                            8           2050 h                                                            9            910 h                                                            5           3680 h                                                           ______________________________________                                    

EXAMPLE 26 Light stabilising effect in PP fibres (130/37)

1000 parts of unstabilised polypropylene powder (melt index ˜18) weremixed in a drum mixer with 1 part ofpentaerythritoltetrakis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate]and with 3 parts of one of the light stabilisers shown in the followingTable III; and the mixture was subsequently extruded in an extruder at220° C. and granulated. The granules obtained were spun in a laboratorymelt spinning machine at a maximum temperature of 270° C. at a speed of300 meters per minute to produce a 130/37 denier multifilament. This wasstretched and twisted by means of a draw twister. The stretching ratiowas 1:5.6 and the twist number was 15/meter, so that finallymultifilaments 130/37 denier were obtained. These multifilaments weremounted on white cardboard and exposed in the Xenotest 1200. Theexposure time until there occurred a 50% loss of tensile strength wastaken as a measure of the protective action of the stabiliser.

The results are summarised in Table III.

                  TABLE III                                                       ______________________________________                                                     Exposure time in the Xenotest                                                 1200 until the tensile strength                                               has decreased to half the                                        Stabiliser No.                                                                             initial value                                                    ______________________________________                                        none         250 h                                                            3            500 h                                                            4            1400 h                                                           6            825 h                                                            ______________________________________                                    

What is claimed is:
 1. A composition comprising plastics subject tothermal, oxidative and light degradation stabilized with an effectivestabilizing amount of a metal complex of the formula I

    (M.sup.9⊕)(L.sup.r⊖).sub.(q-s)/r (B.sup.63).sub.s ·mA(I)

in which M is a metal ion having a double or triple positive chargeselected from the group consisting of Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Zn²⁺,Cd²⁺, Al³⁺, Sn²⁺, Cr³⁺, Co²⁺, Ni²⁺, VO²⁺, MoO²⁺, (R)₂ Sn²⁺, and (CH₂ CH₂COOR)₂ Sn²⁺, wherein R is C₁ -C₈ Alkyl, q is 2 or 3; L^(r)⊖ is a 2-, or3- or 4-dentate chelate-forming agent selected from the categoryconsisting of the groups IVa, IVb and IVc ##STR63## in which u is 0 or 1and R₁₅ and R₁₆ independently of one another are hydrogen, C₁ -C₁₈alkyl, which can be unsubstituted or substituted by a group Va, Vb orVc: ##STR64## or a group Vc, or a group of the formula VI ##STR65## inthe p-position, or halogen or a radical --OR₂₄, or R₁₅ and R₁₆ togetherare a 1,3-butadiene-1,4-diyl radical, and R₅ is hydrogen, methyl orphenyl and Y is hydrogen, oxyl, alkyl, alkenyl, alkynyl, alkoxyalkyl,aralkyl, 2,3-epoxypropyl, formyl, acetyl, acryloyl, crotonyl, or one ofthe groups --CH₂ COOR₆, --CH₂ --CH(R₇)--OR₈, --COOR₉ or --CONHR₉, inwhich R₆ is alkyl, alkenyl, phenyl, aralkyl or cycloalkyl and R₇ ishydrogen, methyl or phenyl and R₈ is hydrogen, formyl, acetyl,propionyl, butyryl, octanoyl, dodecanoyl, stearoyl, acryloyl, benzoyl,cinnamoyl, phenylacetyl, phenylproprionyl or each of benzyl, cinnamoyl,phenylacetyl or phenylproprionyl substituted by chlorine, alkyl, alkoxyand/or hydroxyl, and R₉ is alkyl, cyclohexyl, phenyl or benzyl, and X₁and X₂ independently of one another are --O-- or ##STR66## and R₂₁ ishydrogen or C₁ -C₈ alkyl and R₂₂ is hydrogen or a group --X₁ R₂₆, and Zis --O-- or ##STR67## and R₂₃ is C₁ -C₁₈ alkyl, C₃ -C₆ alkenyl, C₃ -C₄alkynyl, C₅ -C₇ cycloalkyl, C₆ -C₁₀ aryl, C₇ -C₁₄ aralkyl, C₇ -C₁₄alkylphenyl or a group of the formula VI, and R₂₄ is hydrogen or C₁ -C₈alkyl, C₅ -C₇ cycloalkyl, C₆ -C₁₄ aryl, C₇ -C₁₄ aralkyl or C₂ -C₁₂alkenyl which are unsubstituted or substituted by a group of the formulaVc; or R₂₄ is formyl, acetyl, propionyl, butyryl, octanoyl, dodecanoyl,stearoyl, acryloyl, benzoyl, cinnamoyl, phenylacetyl, phenylpropionyl,or each of benzoyl, cinnamoyl, phenylacetyl or phenylpropionylsubstituted by chlorine, C₁ -C₈ alkyl, C₁ -C₈ alkoxy, as group Vc orhydroxyl, and R₂₅ is hydrogen, or C₁ -C₁₈ alkyl, or C₃ -C₆ alkenyl, C₃-C₄ alkynyl, C₅ -C₇ cycloalkyl, C₆ -C₁₀ aryl, C₇ -C₁₄ aralkyl, a groupof the formula CH₂ --CH(R₅)--OR₂₆ or a group of the formula VI, and R₂₆is hydrogen, C₁ -C₁₈ alkyl, C₃ -C₆ alkenyl, cyclohexyl, benzyl orformyl, acetyl, propionyl, butyryl, octanoyl, dodecanoyl, stearoyl,acryloyl, benzoyl, cinnamoyl, phenylacetyl, phenylpropionyl, or each ofbenzoyl, cinnamoyl, phenylacetyl or phenylpropionyl substituted bychlorine, C₁ -C₈ alkyl, C₁ -C₈ akkoxy or hydroxyl, and R₁₇ is hydrogen,C₁ -C₁₈ alkyl, halogen, a group --OR₂₄ or a group of the formula Vc andR₁₈ is a group --N(R₂₅)R₂₇ and R₁₉ is hydrogen, or R₁₈ and R₁₉ togetherare ═O or ═NR₂₇, and R₂₀ is hydrogen, C₇ -C₁₄ aralkyl, C₇ -C₁₄alkylphenyl, or C₁ -C₁₈ alkyl, C₂ -C₁₂ alkenyl, C₅ -C₁₂ cycloalkyl or C₆-C₁₄ aryl, which are unsubstituted or substituted by a group of theformula Vc, or, if R₁₈ and R₁₉ together are ═O, R₂₀ is a group of theformula Va; or R₂₀ is also a group of the formula VII ##STR68## in whichR₁₅, R₁₆, R₁₈ and R₁₉ are as defined above and R₂₈ is C₁ -C₁₂ alkylene,butenylene, C₆ -C₁₀ arylene or diphenylene, and R₂₇ is hydrogen, C₇ -C₁₄aralkyl, C₇ -C₁₄ alkylphenyl, hydroxyl, or C₁ -C₁₈ alkyl, C₂ -C₁₂alkenyl, C₅ -C₁₂ cycloalkyl or C₆ -C₁₄ aryl, which are unsubstituted orsubstituted by a group of the formula Vc, or a group of the formula VIor a group of the formula --CH₂ --CH(R₅)-OR₂₆ ; or, if R₂₀ is not agroup of the formula VII, R₂₇ is also a group of the formulae VIIIa orVIIIb ##STR69## in which R'₂₀ has the meaning defined for R₂₀ with theexception of the groups of the formula VII, and R₁₅, R₁₆, R₂₅ and R₂₈are as defined above, and r is 1 or 2, equal to the number ofcoordinatively bonded phenolate anions in the molecule, B, as an anionhaving a single charge, is an anion of an aliphatic or aromaticcarboxylic acid, of a phosphonic acid half-ester, of a phosphinic acid,of a phosphinous acid or of an enol of the formula IX ##STR70## in whichR₂₉ is alkyl, alkenyl, cycloalkyl, aralkyl or aryl and R₃₀ is hydrogen,alkyl, alkenyl, cycloalkyl, aralkyl, aryl or alkoxycarbonyl, or R₂₉ andR₃₀ together 1,4-butadi-1,3-enylene or 1,4-butylene, and R₃₁ is alkyl,alkenyl, cycloalkyl, aralkyl, aryl or alkoxy, or amino, and R₃₂ is oxoor imino, and the sum (q-s)/r+s must equal q, and m is an integer from 0to 3, the sum t((q-s/r))+s+m being equal to the coordination number ofthe metal ion M, and A is H₂ O or an amine of the formula III ##STR71##in which R₁₂ is alkyl, hydroxyalkyl, or optionally alkylsubstitutedcycloalkyl, aryl or aralkyl, or aminoalkyl which may be substituted by apiperidinyl group, or R₁₂ is a piperidinyl group, and R₁₃ is hydrogen,alkyl, hydroxyalkyl, or optionally alkyl-substituted cycloalkyl oraminoalkyl which may be substituted by a piperidinyl group or R₁₃ is apiperidinyl group; or R₁₂ and R₁₃ together with the N atoms form apyrrolidine, piperidine or morpholine group which may bealkyl-substituted and R₁₄ is hydrogen, alkyl or hydroxyalkyl.
 2. Acompound ##STR72##
 3. A compound ##STR73##
 4. A metal complex of theformula XIV

    [M.sup.9⊕ ][L.sub.1.sup.r⊖ ].sub.q/r ·mA(XIV)

in which M is mg²⁺, VO²⁺, Ca²⁺, Zn²⁺, Co²⁺, Ni²⁺ or Al³⁺ and q is 2 or 3and L₁ is a t-dentate group of the formula IV ##STR74## which issubstituted by at least one group of the formulae Va, Vb or VI,##STR75## and u is 0, 1 and t is 3, and R₁₅ and R₁₆ independently of oneanother are hydrogen or C₁ -C₁₈ alkyl which can be unsubstituted orsubstituted by a group of the formulae Va, Vb or Vc; ##STR76## or agroup Vc, or a group of the formula VI in the p-position, halogen or aradical --OR₂₄, or R₁₅ and R₁₆ together form a 1,3-butadiene-1,4-diylradical, and R₅ is hydrogen, methyl or phenyl and Y is hydrogen, oxyl,C₁ -C₁₂ alkyl, C₃ -C₁₂ alkenyl, C₃ -C₆ alkynyl, C₂ -C₂₁ alkoxyalkyl, C₇-C₉ aralkyl, 2,3-epoxypropyl, formyl, acetyl, acryloyl, crotonyl, or oneof the groups --CH₂ COOR₆, --CH₂ --CH(R₇)--OR₈, --COOR₉ or --CONHR₉, inwhich R₆ is C₁ -C₁₂ alkyl, C₃ -C₆ alkenyl, phenyl, C₇ -C₈ aralkyl orcyclohexyl and R₇ is hydrogen, methyl or phenyl and R₈ is hydrogen,formyl, acetyl, propionyl, butyryl, octanoyl, dodecanoyl, stearoyl,acryloyl, benzoyl, cinnamoyl, phenylacetyl, phenylpropionyl, or each ofbenzoyl, cinnamoyl, phenylacetyl or phenylpropionyl substituted bychlorine, C₁ -C₄ alkyl, C₁ -C₈ alkoxy or hydroxyl, and R₉ is C₁ -C₁₂alkyl, cyclohexyl, phenyl or benzyl, and X₁ and X₂ independently of oneanother are --O-- or ##STR77## and R₂₁ is hydrogen or C₁ -C₈ alkyl andR₂₂ is hydrogen or a group --X₁ R₂₆ and Z is --O-- or ##STR78## and R₂₃is C₁ -C₁₈ alkyl, C₃ -C₆ alkenyl, C₃ -C₄ alkynyl, C₅ -C₇ cycloalkyl, C₆-C₁₀ aryl, C₇ -C₁₄ aralkyl, C₇ -C₁₄ alkylphenyl or a group of theformula VI, in which Y and R₂₁ are as defined, and R₂₄ is hydrogen or C₁-C₈ alkyl, C₅ -C₇ cycloalkyl, C₆ -C₁₄ aryl, C₇ -C₁₄ aralkyl or C₂ -C₁₂alkenyl which are unsubstituted or substituted by a group of the formulaVc, in which X₂ and R₂₃ are as defined, or is formyl, acetyl, propionyl,butyryl, octanoyl, dodecanoyl, stearoyl, acryloyl, benzoyl, cinnamoyl,phenylacetyl, phenylpropionyl, or each of benzoyl, cinnamoyl,phenylacetyl or phenylpropionyl substituted by chlorine, C₁ -C₈ alkyl,C₁ -C₈ alkoxy, a group Vc or hydroxyl, R₂₅ is hydrogen, C₁ -C₁₈ alkyl,which can be unsubstituted or substituted by a group of the formula Vc,in which X₂ and R₂₃ are as defined, or C₃ -C₆ alkenyl, C₃ -C₄ alkynyl,C₅ -C₇ cycloalkyl, C₆ -C₁₀ aryl, C₇ -C₁₄ aralkyl, a group of the formulaCH₂ --CH(R₅)--OR₂₆ or a group of the formula VI, and R₂₆ is hydrogen, C₁-C₁₈ alkyl, C₃ -C₆ alkenyl, cyclohexyl, benzyl or formyl, acetyl,propionyl, butyryl, octanoyl, dodecanoyl, stearoyl, acryloyl, benzoyl,cinnamoyl, phenylacetyl, phenylpropionyl, or each of benzoyl, cinnamoyl,phenylacetyl or phenylpropionyl substituted by chlorine, C₁ -C₈ alkyl,C₁ -C₈ alkoxy or hydroxyl, and r is 1 or 2 and m is a number from 0 to3, the sum (3.q/r)+m being equal to the coordination number of the metalion M, and A is H₂ O or an amine of the formula III, ##STR79## in whichR₁₂ is unsubstituted or --OH-- substituted C₁ -C₁₈ alkyl, C₅ -C₁₂cycloalkyl, C₆ -C₁₈ aryl, C₇ -C₂₀ aralkyl, a aminoalkyl group or apiperidinyl group, and R₁₃ is hydrogen or unsubstituted or--OH-substituted C₁ -C₁₈ alkyl, C₅ -C₁₂ cycloalkyl, aminoalkyl group ora piperidinyl group, or R₁₂ and R₁₃ together with the N atom form apyrrolidine, piperidine or morpholine ring which is substituted by alkylgroups or is unsubstituted and R₁₄ is hydrogen or unsubstituted or--OH--substituted C₁ -C₁₈ alkyl.
 5. A metal complex of the formula XV

    [M.sup.7⊕ ][L.sub.2.sup.r⊖ ].sub.q/r ·mA (XV)

in which M is Mg²⁺, Sr²⁺, VO²⁺, Ca²⁺, Mn²⁺, Zn²⁺, Co²⁺, Ni²⁺ or Al³⁺ andq is 2 or 3 and L₂ is a t-dentate group of the formula IVb ##STR80##which is substituted by at least one group of the formulae Va, Vb or VI,##STR81## and t is 2, and R₁₅ and R₁₆ independently of one another arehydrogen, C₁ -C₁₈ alkyl, which can be unsubstituted or substituted by agroup of the formulae Va, Vb or Vc, ##STR82## or a group Vc, or a groupof the formula Vi in the p-position, halogen or a radical --OR₂₄, or R₁₅and R₁₆ together form a 1,3-butadiene-1,4-diyl radical, and R₅ ishydrogen, methyl or phenyl and Y is hydrogen, oxyl, C₁ -C₁₂ alkyl, C₃-C₁₂ alkenyl, C₃ -C₆ alkynyl, C₂ -C₂₁ alkoxyalkyl, C₇ -C₉ aralkyl,2,3-epoxypropyl, formyl, acetyl, acryloyl, crotonyl, or one of thegroups --CH₂ COOR₆, --CH₂ --CH(R₇)--OR₈, --COOR₉ or --CONHR₉, in whichR₆ is C₁ -C₁₂ alkyl, C₃ -C₆ alkenyl, phenyl, C₇ -C₈ aralkyl orcyclohexyl and R₇ is hydrogen, methyl or phenyl and R₈ is hydrogen,formyl, acetyl, propionyl, butyryl, octanoyl, dodecanoyl, stearoyl,acryloyl, benzoyl, cinnamoyl, phenylacetyl, phenylpropionyl, or each ofbenzoyl, cinnamoyl, phenylacetyl or phenylpropionyl substituted bychlorine, C₁ -C₄ alkyl, C₁ -C₈ alkoxy or hydroxyl, and R₉ is C₁ -C₁₂alkyl, cyclohexyl, phenyl or benzyl, and X₁ and X₂ independently of oneanother are --O-- or ##STR83## and R₂₁ is hydrogen or C₁ -C₈ alkyl andR₂₂ is hydrogen or a group -X₁ R₂₆ and Z is --O-- or ##STR84## and R₂₃is C_(1-C) ₁₈ alkyl, C₃ -C₆ alkenyl, C₃ -C₄ alkynyl, C₅ -C₇ cycloalkyl,C₆ -C₁₀ aryl, C₇ -C₁₄ aralkyl, C₇ -C₁₄ alkylphenyl or a group of theformula VI, in which Y and R₂₁ are as defined, and R₂₄ is hydrogen or C₁-C₈ alkyl, C₅ -C₇ cycloalkyl, C₆ -C₁₄ aryl, C₇ -C₁₄ aralkyl or C₂ -C₁₂alkenyl which are unsubstituted or substituted by a group of the formulaVc, in which X₂ and R₂₃ are as defined, or is formyl, acetyl, propionyl,butyryl, octanoyl, dodecanoyl, stearoyl, acryloyl, benzoyl, cinnamoyl,phenylacetyl, phenylpropionyl, or each of benzoyl, cinnamoyl,phenylacetyl or phenylpropionyl substituted by chlorine, C₁ -C₈ alkyl,C₁ -C₈ alkoxy, a group Vc or hydroxyl, R₂₅ is hydrogen, C₁ -C₁₈ alkyl,which can be unsubstituted or substituted by a group of the formula Vc,in which X₂ and R₂₃ are as defined, or C₃ -C₆ alkenyl, C₃ -C₄ alkynyl,C₅ -C₇ cycloalkyl, C₆ -C₁₀ aryl, C₇ -C₁₄ aralkyl, a group of the formulaCH₂ --CH(R₅)--OR₂₆ or a group of the formula VI, and R₂₆ is hydrogen, C₁-C₁₈ alkyl, C₃ -C₆ alkenyl, cyclohexyl, benzyl or formyl, acetyl,propionyl, butyryl, octanoyl, dodecanoyl, stearoyl, acryloyl, benzoyl,cinnamoyl, phenylacetyl, phenylpropionyl, or each of benzoyl, cinnamoyl,phenylacetyl or phenylpropionyl substituted by chlorine, C₁ -C₈ alkyl,C₁ -C₈ alkoxy or hydroxyl, and R₁₇ is hydrogen, C₁ -C₁₈ alkyl, halogen,a group --OR₂₄, or a group of the formula Vc in which R₂₃, R₂₄ and X₂are as defined, and r is 1 and m is an integer from 0 to 2, the sum(2q)+m being equal to the coordination number of the metal ion M, and Ais H₂ O or an amine of the formula III, ##STR85## in which R₁₂ isunsubstituted or --OH-substituted C₁ -C₁₈ alkyl, C₅ -C₁₂ cycloalkyl, C₆-C₁₈ aryl, C₇ -C₂₀ aralkyl, a aminoalkyl group or a piperidinyl groupand R₁₃ is hydrogen or unsubstituted or --OH-substituted C₁ -C₁₈ alkyl,C₅ -C₁₂ cycloalkyl, a aminoalkyl group or a piperidinyl group, or R₁₂and R₁₃ together with the N atom form a pyrrolidine, piperidine ormorpholine ring which is substituted by alkyl groups or isunsubstituted, and R₁₄ is hydrogen or unsubstituted or --OH-substitutedC₁ -C₁₈ alkyl.
 6. A composition comprising plastics subject to thermal,oxidative and light degradation stabilized with from 0.01 to 5% of acompound according to claim
 5. 7. A process for stabilizing plasticsagainst thermal, oxidative and light degradation which comprisesincorporating into said plastics from 0.01% to 5% of a compoundaccording to claim
 4. 8. A process of stabilizing plastics againstthermal, oxidative and light degradtion which comprises incorporatinginto said plastics from 0.01 to 5% of a compound according to claim 5.9. A composition of matter comprising a plastics subject to thermal,oxidative and light degradation stabilized with from 0.01 to 5% of acompound according to claim
 4. 10. A process of stabilizing a plasticsagainst thermal, oxidative on light degradation which comprisesincorporating into said polymeric material from 0.01 to 5% of a compoundaccording to claim 5.